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, SOME BASIC CONCEPTS IN CHEMISTRY
1. Some Basic Concepts in Chemistry
'I /1-1i69
€omp€tition Focus l no-1192
Addllloial U3€lul hlornreilon
in
1n9
Multlplo Cholct Oue6tlons 1184
Addltlonal Ouesllon6 1/9'l
OF MATIER
'w@iE
R 211-2J53
ol Matter
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Fcu 2J54--2178
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Conpcthlon
Arftload tkdul Hoantaton 2154
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216/8
A.lfitqd Oq.do zn
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EGIUITIBRIUM--.I
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EQUItIBR.IUfrI--II
(lonic Equilibrium in Solutions)
8. Equilibriunr{l (tonic Equilibrium in Sotutions)
Conpctition Focus
A,rldltonal Us.rul lnlbiluUon 8/60
C.B.S.E. P.M.T. (Mains) Speciat 862
l.l.T. (Mains) Speciat 8158
lluttplc Cholce Omctlons 8y80
AdltlorEl Ouertlom 8/90
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-"..-
REACTIONS
9. Redox Reactions 911-9151
FI\TDROGEN
11. Hydrogen
Compctition Focus
Addhlonal Usstul lniornatlon 11145
C.B.S.E. P.M.T. (Mains) SPecial 11147
l.l.T. (Mains) Special 't114nB
irultlPle Cholce Ouestlons 11/50
Addltloflal Ouestlons 1 1/5it
.S.BLOCK
E1EMENTS
12. s-Block Elements 1211-12151
HYDROCARBONS
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15. Hydrocarbons
15fi- 15/106
Competition focus 151107-15t134
Addft ional Usefu I lnlbrrEuon 1yl07
C.B.S.E. p,M.T. (Mains) Speciat 151112
l.l.T. (Mains) Speciat 1y118
Muhlple Cholce Ouesdong 15t120
Addiilonal Ouesdons 1si/l31
Corpetition Focus
Addftloml Useful lniomaUon 1d49
C.B.S E. PM.T. (Mains) Speciar 16i/50
l.l.T. (Mains) Speciat 16152
ilultiple Choice eue.fions 16i/56
Addltlonal Quesfions 16/61
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Conpetition Focus R
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Addtlon l t lclul lnlonftttlon 1A^l4
C.B.S.E. P.M -T. (Marns) Special 1A,:ls
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APPENDICES
Appendix 1. - lmportant Name Reactions (ln Alphabetical order)
Appendix 2. - Distinction Between Pairs of Compounds
Appendix 3. - SomeTypica! Conversions
t@ TABI"ES
LogTables (i)- (iv)
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Conc rrti=tr3r
IMPOR'TANCE OT' STUDYING CHEN{ISTRY accuracy. Further, as chemistry deals with all sub-
starces present in our body and all those present
IIT
ur
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112
Pradeep's
(i) It has provided chemicol lertilizers sach as (vi) Synthetic vitamins and ronics have con-
urea, calcium superphosphate, sodium nitrate, am- tributed significantly towards bettor health.
monium sulphate etc. which have increased the In fact, the use of more effective medicines,
feld of crops and fruits. vitamins etc. and better sanitary conditions have
(ii) It has helped to protect the crops from helped to incrcq.se the average life span.
insccts and harmtul bacteria by the use o[ certain (3) Saving the enviroDment. Refrigerants like
elfcctive tsecticides, fungicides ar,d pesticides- chlorofluorocanbons (CFCs) which destroy the
(iii) The use of presenatives has helped to ozone layer have been replaced by environment-
presewe food products like jam, butter, squashes friendly chemicals. However, Green house gases
etc. for longer periods. like CtIa, CO2 etc. are still posing a challengc to the
(rv) lt ha.s given me thods to lest the presence of chemists.
qdulterdlts thereby eo"suring the supply of pure (4) Increase in comforts, pleasurts and
food-stuff. luxuries. Chemistry has placed a large number of
(2) Contribution to better health and sanita' utility goods at our disposal which have added to
tion, Chemistry has contributed towards better our comforts, pleasures and lururies. A few ofthese
health and sadtation in a number of ways as fol- are given below :
lows : (i) Sythetic fbres (cloth). ID' addition to the
natural fibres like cotton, wool, silk etc., chemistry
has helped in the production of synthetic fibres
such as terylene, nylon, rayon etc. which are more
comfortable, durable and attractive. They are easy
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to wash, dry quickly and do not need ironing. Fhr-
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past. ther, chemistry has provided a large number of
Similarly, life saving drugs llke platin al'd synthetic dyes which impart bright aad fast colour
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cis
,arol have been found to be very effective for ca.ncer to the clothes. It has also provided chemicals to
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therapy and AZT (Aziodothym.idine) is used for make these clothes fue-proof and water-proof, if
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animals and plants or by synthetic methods. (ii) Build.ing mateials. By supplying steel and
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pound) and coated with suitable chemicals. usefulbut disposal ofnuclear waste poses a serious
Similarly, fire-works which amuse us on festivals problem to
humanity. S
and marriages are chemical products. Phonograph records have added to our
records used for listening music are made of music but they are made
polyvinyl chloride, a chemical compound. produced from vinyl chloride which can cause liver
(5) Thansport and commuuication. Almost cancer in industrial workers. Antibiotics have
all means of tran^sport inclurling automobiles eliminated infectious diseases but their overuse is
(scooter, cars, trucks, buses etc.) aeroplanes, very harmfu l. Likewise, insecticides h ave increased
helicopters, railways use either petrol or diesel
(petroleum products) or coal which are all chemi-
p
cal
Cuality
fuels of ap-
polo Mars. sugar etc. which are proving a curse to the society.
Knowledge of chemistry has also helped in the
Thus though chemistry can be regarded as
development of telephone and telegraph as impor- greatest benefacto
tant means of communication.
be a blessing or a c
(6) Nuclear or Atomic energF. In view of the the uses to whichit
decreasing coal and petroleum resources, the is maintained between benefits and problems
energy crisis. caused by progress in chemistry.
by providing an
s 1..("1't()N_il
nuclear energy.
tion of the com- R N{I]AS UREI\{ENTS IN CHI'I\TIS TRY
pound, uranium hexafluoride, made possible the \
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1.3. Physical Quantities
enrichment of U-235 which was usLd first for i: :i:::ii:::::::::::::i.:i:::i::::::i:::::::::::::j:j:::::::.:::::::::
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making atomic bomb and later in the nuclear reac- In everyday life, we come across a number of
ctricity. Nuclear energy can
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ables in kilograms,
diggr"C tunnels, blasting
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c. However during
g as well.
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the measurements
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Applications in industry. Chemistry has of mass, volumes and lengths, we come across the
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played an important and useful role towards the measurement of a number of other quantities such
clevelopment and growth of a number of industries as temperature, pressure, concentration, force,
work, density etc.
All such quantitics whiah we come across during
our scientifrc studies are callcd physical quan-
tilies.
Evidently, the measurement of any physical
Similarly, it has helped in the spthesis of new quantily consists of two parts :
materials having specific magnetic, electrical and
(i) the number, ernd
optical properties which are used in the production
(ii) the unit.
of
. superconducting ceramics, ionducting
polymers, optical fibres etc. For example, if an object weighs 4.5 kg, it
(8) Applications in war. Chemistry has also involves rwo parts : (i) a.-5 i.e. the number and
increased the striking power of man in war times. It (ii) kgi.e. the unit.
Thus the main aims of this section are :
(rrr) Ii, derive the units of any physical quan- for reporting scientific data and gradually most of
tity and to check the accuracy of any scientific the countries have also switched over to this system
equation by seeing that the dimensions of both sides for measurements of everyday use. India started
of tlre equation are same i.e. concept of dilnensional following metric system since 1,957.
analysis. The metric system, as put forward earlier, was
further imporved by the General Conference of
Weights and Measures (Conference Generale des
,,A, ,:.,
Poids et Mesures, CGPM) which met in October
lo ,,,.,, 1960 in France. The improved system of units has
Since early times, different types of units of been accepted internationally and is called Interna-
measurements have been very popular in different tional System of Units or in short SI Units (for
parts of the world e.8'. sers, pounds etc. for mass ; Systeme Internationale iu FrencQ.
miles, furlongs, yards etc. for distances. However With greater accuracy in measurement, the
these units are quite cumbersome because of no 'unit' definitions and hence the system of units is
uniformity in the conversion factors involved e,g. improved from time to time. To maintain uniformity
1 mile : 1760 yards, 1 yard : 3 feet, 1- foot : all over the world, each nation has National Metrol-
12 inches. ogy Institute (I.[MI). ln India, this responsibiliry has
ln view of the diffrculties mentioned above, been assigned to National Physical Laboratory
French Academy of Science, in L791, introduced a (NPL), NewDelhi.
new system of measurements called'metric system' Seven Basic Units. The seven basic physical
in which the different units of a physical quantity quantities on which the International System of
are related to each other as multiples of powers of R
Units is based, their syrrbols, the names of their
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7O, e.g. L km : 1(P m, 1 cm : 10-2 m etc. This units (called the base units) and the symbols of
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system was tbund to be so convenient that scientists these units are given in Thble 1.1.
all over the world immediately adopted this system
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I-ength I metre nl
Mass nl kilogram kg
Time t second S
The SI unit of mass viz. kilogram has been detincd as the ntass of platinunriidium (Pt-Ir) cylinder
that is storecl in an uirtigltt jar at htteruational Bw'eatt of Weights ancl Measures in France.
Tlre Sl unit of length viz metre was originally defined as the lengtlt between two marks on d Pt-Ir bar
kept ut a temperatlo'e oJ' 0'C (273 K). However, now it has been redefined by CGPM as the length of the
path trove llecl b, tight irt vuarunt duing a tinrc intcnal r[ 11299,792,458 oJ' a second.
Though the S.I. unit of temperature, 'kelvin', yet it is very common to express temperatures in degree
celsius ('C). The two are related to each other as
oc + 273'15'
Tempe.iiuro in degrcc kelvin (K) = Temperature iu
Howcver, it may be remembered that size of l"K : size of 1"C.
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SOME BASIC CONCEPTS IN CHEMISTRY 1/s
Similarly, though the S.I. unit of length is metre, yet it is very common to express length in Angstrom
(A) or nanometres (nm) or picometres (pm). These are relaterl to S.I. unit as follows :
1 A = 10-10 rn, lnm : l1-s m, 1pm : 1O-12 nt
Rtrther, it is important to understand that the term 'weight' should not be used ln place of .massr.
Thcv have differcnt meaning. Mass is the quantity of matter contained in the sample and for the given
samplc, it is constant and does not depend upon the place. Weight is the force with which the body is
attracted towards the earth (W : t"S).Thus, it depends upon the acceleration due to gravitv g'which
varies from place to place.
Derived units. The units of all other physical quantities arc clerivcd out of thosc of the basic physical
quantities. The units thus obtained are callcd the derived units. Some commonlv used physical quantities
and their derived units are given in Thble 1.2.
TABLII 1.2. some conrmonly used physical quantities and their derived unit
per second
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- _t
(Newton per sq. metre) =kgm -l
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*Newtonisdefinedastheforcethatgivesamassof lkganaccelerationof
lms-2sothat f = ma = (lkg)(1 ms-2)
=.lkgms-2=1N.
*+Jouleistheworkdonewhenadisplaccmentoflmetretakespla-cebyaforceoflnewtonsothatw=fxd=(1
N)(1 nr)
= (lkgms-2;1tnr; = I kgm2s-2 = lJ. ThustJ:1Nm= 1L*'-2.-i.
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116 . ,t.t ).t; ! Neu, Course ChemistrrllffiID
dcci d 10- I
l decimetre(dm) = 10-l m = 0 1 m
cenll c 702 centimetre (cm) = l0-2 tt't = 0 01 t'tl
mrlli n] 10-l 1 millimetre (nrD) = 10-3 m
t'lllcro 10-6 1 n]icrometre (rrn) = 10-6 D]
nat'to n l0 e
I (nm) = 10-9 m
DaDometre
12
prco p 10- 1 picometre (pm) = 10-12 n'l
zella Z 1021
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As volume is very often expressed in litres, it 2. Symbols o{ the units do not have a plural
is important to note that the equivalence inSI units ending lile 's'. For example we have 10 cm and not
10 cms.
:
I litre (1L) 1dm3 3. Words and symbols should notbe mixed e.g.
we should write either joules per mole ol J mol-l
and I millilitre (l ml) : I cm3*
) and not joules mol-1.
4. Prefixes are rrsed with the basic units e.g
Som€ lmportant Points to kilometer means 1000 m(becau-se meteris the ba-sic
Remember About S.I. Units unit).
l. The unit named after a scientist is started Erception. Though kilogram is the basic unit
with a small letter and.ot with a capital lctter e.g. of mass, yet prehxes are used with gram because in
unit ol force is written as ncwton and not as New- kilogram, kilo is already a prefix.
ton. 5. a power is
Likewise unit of heat or work is written as a power eans (ccn-
timeter)
iortle and not as Joule.
*From 1901 to 19f)4, a litrcnl"as defrncd as the lolumc of 1 k8 ofwater at 4"C. During this pcriod, a millilitre was very slightly
largerthana cubic clntimetre.Ill 1!b4, the litl! \r"a6 rEd.fincd as era.tlyequalinvolumc io 1m0 clbic centimetr€s, theEby removing
the confusion.
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SOI\,IE BASIC CONCEPTS IN CHEMISTRY 1n
1.5. Precision and Signilicant Figures ii::+ititi:ijti:iitiiU;iiri: accurate than pacing off a length. One method to
1.5.1. Dilference betw€€n Prccision and Ac-
curacy.
whole
banana
r.c. l.hey consist ofara ct numbers. Similarly, defined tlte conect value, tlrc measurenenl is said, to be
accurate (the individual meq$urements may not be
close to each othe).
If the values of different meosurcments qre close
to each other ond hence close to their ayerage value,
the measurement is said to be precise- (The average
(i) the accuracy ofthe measuring device used, value of different measurements may not be close
and (ii) the skill of its operator to the correct va.lue). Tte precislon depends upon
the measuring device as well as the skill of the
asure the lengih
operator.
it off. If we pace
count each time For example, suppose the actual length of the
or to hav left over. Thus the room is 10 . 5 rz . Four different person^s report the
result of xactly correct. Ac- result of their five mea.surements as follows* :
curacyis way the measure-
meot is measure is more
Measurement (m) 1, 2 3 4 5 Average (z)
Person A 10.3 10.4 10.5 10.6 10.7 10.5
Person B 10.0 10. 1 10.2
R 10.3 10 4 70.2
Pcrson C 10. I 10.3 10'5 to.7 10.9 10.5
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and precise.
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Conecl
Measurement byperson C has poorprecision
.hut good
accuracy (ust by chance/luck)
. Measurement by person D has poor accuracy
and poor precision.
. These results may be represented diagram-
matically as shown in Fig. 1.1. (a) (b) (c) (d)
Both Poor Good Poor
accurate a@uracy accuIacy accuftlcy
and but good but poor and poor
prccrs€ precision paeclsrcn preclslon
0ust by luck)
FIGURE f ,1. Understanding accuracy and prechion.
mistake is made r
ermrs. They do not
affecl the accuracy
this means that the actual mass of the object is For example, 10500 g may have three, four or
14 -5678 '+0 0001 g i.e. it lies between 14 567'7 ar,d five significant figures. This ambiguity is removed
14 5679. Thus in the expressed masi, the first live by expressing the value in an exponential form. For
digits are certainbutthe last involvos anuncertainty example, the above mass may be written in three
t
of 1. All measured quantities are reported in different exponential forms as follows :
such a way that only thc last digit is uncertain 1 05 x 104 g, which has ,rrree significant irgures
(usually by t l). or I 050x 104 g, which has/our signiEcant figures
Tlu aulnutnber o! tligi* in a nwnber induding or 1 .0500x 104 g, which hasfve signitrcant figures
the la.lt digit whose vafue * uacerlein is ca eiltlu In these cases, the significant figures of on.[y
nunher oJ sigrtifica frgures. the first factor are counted (remembering that all
zeros to the right of a decimal point are signifrcant).
For example, in the above value i.e. 14'56789, Thus in such cases, the general notation is
there are six signihcant figurcs. Similarly, the num-
ber 2 5 has two significant figures while the number
Nx10'
2 014 has four signiEcant figures. where N : a number with a single non-zero digit
1.5J. Rules for determining the number of to the left of the decimal point
signllicant ligures. The following rules arc applied ard :
n an irrteger.
in determining the number of significant figures in The above method of expressing a number is
any rcported quantity :
called Scientilic or Exponential Notation.
Rulc I. All non-zero digits u^s well us 1.5.4. Rules for determinlng th€ numb€r of
hefueen the non-zero digils signilicant ligures in answers involving calcula-
tions. To get the final result of any experiment,
576 cm has thrce signihcant figures usually calculations are required which involve ad-
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0 48 g has two signiltcant figurcs dition, subtraction, multipiication ind division of
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5004 has bur significant figurcs different numbers. These numbers may have dif-
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Rule 2. Zaros to lhe lelt ol lhe rtr non-zero digit result involving these numbers, therefore, cannot
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in a number ue nol signilicunr. (Thq simply indi' be more accurate or precise than the least precise
N
c.g. {) 05 m has only one signiltcant figurc ber of significant hgures in the answer of any par-
0 (X)45 kg has trvo signihcant figures. ticular calculation :
one alccimalplacc. The digit at the sccond decimal place is 6*,hich is greatel than 5. Hence the di8it at the first plaoc lras
-fhis method is callcd rrutldin' ofi Thc gcneral
been incrcasad by 1. Procedlrre for munding off is as lollows :
(i) If the digrrjust next ro the last digit to be retarned is less thJn 5. the Iast digit rs taken as such and all other diSits on its
right are dropped.
(ii) If rhc di8il js greater than 5, the last digit to be .etained is incrcased by I and all other di8its or its right are droPPed.
(iii) lf the digil rs eqral to 5, the last signilicant figure is teft unchangcd if it is e!,en and is increased by I ifit is odd
ExAlul'LFIS:/ 2.11 =I 21. 1 23(t =1 24, 1 235 - 1 21' I 225=122'
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SO[,4E BASIC CONCEPTS IN CHEMISTHY 119
First number has three decimalplaces, second Thr: first number has four significant figurcs
has one and third has two. Hence a-nswer should be while the second has two. Thc actual product has
reported onlyuptoonedecimalplace. Notethatthe been rounded off to give a reported proriuct of l2
significant figures in the three numbers are 4,2 and i.e. containing rrvo signilicant figurcs only. This is
3 respectiYely. becausc thc lcast precise tcrm in the calculatirrn
.621 (viz. 2 8) has only two significant figurcs.
Exumple 2. 7
6.243
Exunryle 2. 0 4(, +- 15 734 gives
Actual quotient : 0.029236
tom
Actual sum : 14.884
Reported quotient should bc 0 02!) contain-
ing only two significant figurcs bccausc thc lcast
Reported sum = L4.884 precise term in calculations (r'iz. 0 216) has two
Each number has tbree decimalplaces. So the significant figurcs only.
answer is also reported upto three decimal places. It may be noted that both the above rules, in
Further note that the significaot figures in each of fact, may be interpreted as follorvs :
the three numbers is 4 but result has five significant
tigures.
.
r'rTht reported answer should not be more precise
lhqn thc least precise lcrm used in lhc ctleulu-
Exantple 3. 154.2 lion."
6.1
This generalization helps to check the
23 reported ansu'cr in cascs whcrc doubt ariscs. Frr
Actual sum : 183 3 example, in cxamplc 1, the precision ol l.hc lcasL
Reported sum : 183 precise lerm is0 lpart in 2 Ri.,. l prrrt in 2li'r
nearly 35 partrpo- lhousand (i.c. 3-i p.p.t). Thc
The last number is an exact number (invoh'ing R
precisiun ofthe reporlc(l answer is I purt in l2 oi
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no decimal place), Hence answer is also reported
nearly 83 p p-t. Thus the reported resul[ is not more
as an cxact number.
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Actual DifL 12.4775 more precise than thc least precise term- Henca thc
N
As the sscond number has two decimalplaces Rulc involves a numher ol steps,
onlywhile the first has four, the answer is reported the resuU shouA mntuin the same flumber of sig-
upto the two dccimal places only. nilicanl Jigwet o-t lhot oJ lhe kost precise number
involved, other than,h.e exuct numben.
Exantple 5. 29.25
12.0234 Erample.
- 12-961 x 0.02435 :
Actual Diff. : 17 2: 6 0 7(192988
Rcported Diff. : 0.4 x 4
77 23
(Actuul result)
As lhc Iirst numbcr has two decimal places Lcaving thc cxact number 4. thc loast precise
only whilc the second has four, [hc ansrver is term has trvo significant figures. Hencc aftcr rouncl-
rcported onlv upto two decimal places. ing off, the reportcd rcsult willbe 0 77r.c. contain-
Rult 2. Tfu rcsuk of u multipliculion or division ing two significaot figl:res. Altctlluti t,c/y., thc abovc
shoal.d he repo ed lo lhe same number oJ sig- rulc is applied as follorvs:
nificant.figures us is possessed by the lcasl prec(se Fitfi tha number of signifrcantfrgures tlwt the u6lter
krm .,li(:d in Lhe calcuk tion. sbuAcontainisdctirlctl ( it. it shotdil beequlrl to thdl
Etcutnple 1. of the lan:s precire term, orhfi lhan the qact namber).
4.327 Beforu catrying oa the nwthefidlical operutions,
x 2.8 every rurmher is roundd off ln conbin om sipifimnt
Actual Product = 72-7156 figure nore lhan the unswq would lwve. Tfu unflccr
obuind is ihen rouruleil ofi to conrain thz required
Reported Product :12 number oJ significant tigures-
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1110 lccp's Neu, Course Chemistrg$Il)
Thus in the above example, the answer should REMEMBER
have two significant figures. Hence everynumber is
Thc rules lhat h.ave been sto.led above apply only to
first rounded off to contain three sipificant figures.
non-inlegral measured quanlilies because only in
Thus
lhese cases the uncertainty in meu^surement hus
43.0 x O.0243
:0'7683088 signiftsance. These do not apply to exact numbers
0.3210 x4 where uncerlsinty hru no significance e.g. there are
exacl 12 egs in a dozen qf egs, lhere qre exact
After rounding off to two significant figures, 1000 g in I kg, lhere ure exact 3 .feet in I yurd and
reported answer should be 0 .77 .
so on.
1..\ \\i;'t i I Wrat is the difference be- (vi) Three because the reported sum will be
t'vveen 5.0 g and 5.00 g ? only upto one decimal place i.e. 18.9.
_S_glU!&r.Though they look to be equivalent (vii) Two because the number with least num-
bnt scientifically they are different. 5.0 g has two ber of significant figures involvcd in the calculation
significant figures and hence its precision is 0.1 (i.e. M) has two significant figures.
part irr 5 i.e. 20 p.p.t. -5.00 has three significant '\ Express the Jbllowing to fow'
figtrres and hence its precision is 0.01 parts in 5 i.e. significant ftgures :
2p.p.L. Hence -5'00 g is more precise measurement (i) 6.4s372 (ii) 48.382s0 (iii) 70000
than -5'0 g.
(iv) 2. 65986 x ]F Q) 0. 004687.
L \ \\ II 'l li l. How many significant figures are Solution. (i) 6'4s4 (r,) 48.38
tltere in each oJ' the following numbers ?
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(rr,) 7.000 x 104 (iv) 2.660 x tG
(i) 6.00s
(v) 0.00a687.
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(iii) 8000
6'54259 and has a density of 8.8 glcm3. mat is the
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(v) n
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not significant. nificant figures, the reported result should have two
(iri) When expressed as 7'5 x ld, ony significant significant figures.
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figuras of 7 .-5 are to be considered. (u:a) Leaving exact number Z the least precise
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(rv) Apply rules given in Hints (i) and (n) above. term (8. 1) has turo significant figures.
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1112 NeuJ Course Chemistrrl
I .6. Di mensional Analysis .::::::::::ii:::i::::iri,i::a:::!:iii;!:!:::::i:i:i
Note. Ifthe conversion factor were not cor-
rectly used, the answer would have absurd units e.g.
Any calculation involving the use of the
if we write
dimensions o[ the different physical quantities in-
volved is called dimensional analysis.
1751b= 175lb x2'295lb
It is used for any one of the following pur- 1kg
poses:
the answer will have the units tb2 kg- 1
.
(1) Tb convert a physical quantity given in one
type of units into some other units. It consists of llx.A,l\ll'l.li 2. How many inches arc tltere in
the tbllowing steps : 3'00km?Giventhar lknt: 1000m, 1m: 1'094
(i) Fint derctmine the 'unit conversion fac- yd, 1 yd : i6 in.
torlfactors'. Solution. The unit conversion factors will be
e.g,. for conversion of pounds (1b) into 1000 m 1km
:1ooo-
kilograms (kg) or vice versa, 1kg : 2'205Lb. l= 1km
2.205Lb
-r:-
1kg
or , - l'094Yd -
lm 1'094yd
Similarly, for conversion of inches into cm or
36in 1vd
- 1yd _
,' _
vice versa,
- 36in
tinch = 2'54cm
-l:.-.-_----or
2'54cm Here the conversion involves a number of
' f. inch steps. Hence the unit conversion factors are ap-
The quantities such as2'2051b per kg or 1 kg plied in such a way that the units of the preceding
R
EE
per 2' 205 lb, 2 ' 54 cm per inch or one inch per 2 ' 54 factor cancel out. Thus
cnr etc. are called 'urtit conversion factor,s'.
AR
3'00 km : 3'00kff +H
(ii) Multiply the given physical quantitywith the "
C
in
ltlry.ricol quantity as well as that of tlrcunitconversion
N
-r^- l_yd
IA
10s in.
lactor has not been used correctly, the answer will
come out to be in wrong units. Note that the answer has been reported to
contain three significant figures (because 1000 m
(iii) If the
conversion huolves a number of
and 36 in. are exact numbers).
stcp,s, each conversion lactor is used in such a way II)LAN I l' l,l'- 3. Expre s s the fo llowing in S. I. b as e
that tlrc units of the prececlingfactor cancel out.
units using power of 10 notation (example 2'54 rum
As an illustration, a few examples are given : 2'54 x I0-3 m)
bclow:
L\ \1. I t'l.l . : A man weig,hs 175 |b. Express
(a) 1'35 ntm (b) I day (c) 6'a5 mL (d) a8
Itis rt'cigltt itt kg. Given that I kg : 2' 205 lb. pg (e) 0'0426 in (N.C.E.R.T)
(b) S.L unit of time is'sec' (s) lotql mass of o ing in grants and kilogrotns which
ldaY= contsins 0'500 carat diamond snd 7.00 grant gold.
24 hours f)0 miri 60 s (N.C.E.R.T,)
r oay x ------'. ,lhour"
l ryin Solution. The unit conversion factors to be
usedGif6i_
=86400x104r
(c) S.I. unit of volume is 'n3' t_ lcarat _ 3'168grains
' grains I carut
3. lb8
(r.45 mL = fr.45 mL x I Tl . I gram l5'4 grains
IBL ' 15.4 grains I gram
1m x lm lm
" roo* roo.-' ,0,,a- o. soo carar = o.soo erft " a#Hf
= 6 45 x 10-6m3
I rlram
(r.l) S.l. unit of mass is 'kg'
'lo-6g, lkg " t5io"*.
4Eut!= ''
48 uP,
-" tts " ltM)el-
' = 0. 10 gram
.. Total mass of the ring
= 4.8 x t0-t kg
(c) S.I. unit of length is 'm' = 7.00 + 0.109 = 7. t0r
units are then cancelled in the same mamer as the analysis, veib the vqlidity oIthelollo, ingequotiotts:
IA
l. Corlvert 16 I km to miles using the following unils 0i) 1 fg (mass of humaD DNA molecule)
cquivalenLs: (NC.E.R.7:)
I kfl = lmn m, 1 ft = 12 inches
(i, 10-rt
I \'rs (i) 5 x 10rs kg kgl
I m = 100 cm. 1 mile = 1760 yd
5. Convert the following iDto metre
I inch = 2 54 cm, 1yd=3ft [\n' 10 0m'les] (i) 40 Em (thickoess of Milky way galaxy)
2, What rs the weight in pounds of a Sold bar 12 0 (ii) 1 4 Gm (diameter ofSuD)
iDches long,6 ff) inches wide and 3 00 inches
(iii) 41 Pm (distanc€ ofnearest star)
thick? The clensity of gold is 19 3 g cm-3. Given
(N.c.E.R.T.)
I inch = 2 54 cm, 1 lb = 453.6 g. J \ns. 151 lbl
3. fkpress the following in SI unlts : l,\ns (i)4xrOet1, (ii)1.4x109a(iii)41 x 10rs mt
(i) 5'6", thc average height ofaD Indian man. 6. Using the unit conversion factors, express
(ii) tto Driles per hour, the average speed ofa road- 0) l.54ornrr'lntopnrl(r'
wala bus.
(ii)2.66 g cDt-3 to ps pn-3. (N.C.E.R.T.)
(iii) 100 pounds, lhe average weiSht of an lndian
girl. (Tike 1 tu = 4549) I \ns. (i) 1.54xld p-7."-11i4 2.66110-u pg p^-'l
(iv) - I0'c, the lowcst temperature in SiDtla- 7. Vanadium metal is added to steel to intpart
average consumption oI a
(r) 2 lilres ot milk, lhc strength. The density ofvanadium is 5 96 g/cnl3.
family of 4 persons. Blpress rhis io S.I. uDits
R (kg/ra). N.C.E.R-T)
(vi) l4 pounds per square inch (atmospheric pres-
EE
I,\ns 5960 kg/r,t3l
sure)
t. "The star of India" sapphire weiShs 563 carats. If
AR
| \ir- (i) l 6tlrl (ii) 35.tms-r (,ir) 45 4k* one carat is equal to 2m mg, what is the weight of
C
(iv) 263 15K (r)2dm3(v09E41 3kg,' -21 the gemstooe in grams ? (N.C.E.R.T.)
S
tl.,!j.Jil,ff5-,,;G' .T.,,,D,,
looo mg
linch :2'54cm 1 lb :
S
453.6 s
N
I quart : 0'9463lttre
IIT
r A : 1o-rom l atm
= 1::,T;:::'*--,
: 1.013 x 106 dynes/cm2
l bar : 1d Nm-2 :
1d pa
1a.m.u. : L.66053 x t0-27 kg 1mm or 1 torr : 733-322Pa or Nm-z
t"C=t+273.75K
=t+273K calorie :
1 4.L84 J
1 litre : 10-3 m3 : I dm3 1 erg : 10-7 J
1 dyne : 10-s N l electronvolt (eV) : 1.6022 x 10-1e J.
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vl16 i,1 ,,1.1 't Neur Course ChemisttalifrlD
-l'he
SI unit ol. lenlperature. viz. Kelvin was given in honour of the great British scientist 'Lord Kelvin'
'Tbrrrpcratures in Kelvin irre expressed as 25 K, 35 K etc. and not as 25"K, 35"K etc.
Irern:i is a unit oI length usecl in Nuclear Physias. 1 F-ernri = 16-13 cm : 10-ls rr.
Physical Chemical
Classitication Classification
R
EE
AR
C
S
Innrgauic
N
Compounds
IA
IIT
and plants.
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SOME BASIC CONCEPTS IN CHEMISTRY
./n6
The various characteristics mentiooed in thc
heir solubility in
definition of 'mixture, can be explained taking the
dissolve in carb-
cxamplc of a mixture of iron fiI'ings, sulphur-and
common salt. Firstly, they can be mixed in any salt is soluble irr
water. So ary one of the two ca! be dissolved and
propottron. Secondly, the mixture can be tested t; then filtered.
1.12. Difference b A nd
_and A Mixtu iit;i rn:r.i:r;;:j+i:::.:.i,:;:::::ii:i
mixlures are 7.
usually Dot sharp.
S
N
IA
IIT
,KN.(},WLE.P.@:8, )
20 carat gold is a mHru re of 20 pans by weight of gold and 4 pans
by weighr of copper. i Id is 24 caral.
Iodized salt used as a table salt is a mxture of NaCl and a small
amount of Nal.
Cement is a mixlurc oIa number of silicates
'lhe cxistence ofan element in two
or more chemrca,y simrlar bJl physica,y diffcrent forms
and the drffcrent forms arc called a,oiropes e.g d'iamond, g.u'pfr1r", is callcd arotropy
allotropes ofcarbon.
*l charcoal, lamp bla"k ;;.;;
'l-hc exrstencc ofa compound
in diffcrenr crysrafline forms rs ci,ed porymorphism
called polymorphs e.q. ZnS has rwo polymorphs called and rhc differenl forms arc
zinc bleno.'unO ,ruririt".
:ti+ o. lhc exlstcnce of diffcrent \ith slmirar chemic{r comF)sition in the same crysralrine form
e.s. znso;.7 -;;;" "
:::i1*n1.. rr2o aDd Feso;, iro'
'omrx)und\ irornorpo.. simjlarry,
is calrcd
atums,
IM2SO4M2, (SC)4)], 24II2Ol, are isomorphs.
Subsl.ances which absorb mosrure from thc air are calle.d hyBroscopic substaoces ag.
CuSOa, PzO5, quicklime (C.aO) erc. aDhldrous
5. Law of Combining Volumes (Gay Lussac's ly in the two timbs of the Landoll's tube (Fig. 1'2)'
ih" ti-b. were then corked and the tube was
S
1. What mass ofsilver nitrare will react with 5.85 g of 12.0 g. Show that thcsc obscrvations flre in agrce_
sodium chloride to produce 14.35 g of si-lver ment wilh the law ofconservalion of mass.
chloride and 8.5 g of sodium nitrate, iathe law of
conservattoD of mass ts true ? [.\lrs. 17.0 g] {N.C.E.R.T)
2. When 4.2 g of NaHCO3 is added [o a sotution of 3. If
6.3 g oI NaHCO3 arc added ro 15.0 g of
acetic acid (CH3COOH/ weighing 10.0 g, ir is ob_ CHjCOOH solution, thc resrdue ts found to weigh
served that 2.2 gofCOz is released iDto the atmos- 18.0 g. Whar is ll., mass of CO2 released in rhe
phere. The residue left behind is found to welgh reaction ? (NC.E.R.T.)
L\ns.3.3 gl
I
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16
1.15, Law ol Constant ComPosition orygen, combined togcther in the samo hxed ratio
of12:32orj:SbYmass
Heat
(a) CaCOj CaO + CO2 t
(b) C + 02- Co2 t
(c) CaCO. + 2HCl.'.'.....- CaCl2+CO2 t +H2O
Ileal
(d) 2NaHCOi .........-NazCO:r + CO2 t + H2O
:
combines, the ratio of C : O is 12 : 32. But if C-14
isotope combines, the ratio of C : O is 14 :32'
The
(2) rc in the same
the
rqtio but aY be different'
For example CTHTOH aod
CH3OCH3 (both having same molecular formula
viz. CrHuO) the ratio of C:H:O : 24:6:16 =
R
12:3:8bymass.
EE
C ON STANT c OM POSlrlo N
Fw"pffip..r,D* LAW OF
AR
C
witlt to\i-i Uoap"'*i* TbOS in both the samples of PbO2 is identical' the aDove
N
IA
Leadperoxideisalsoplo&lcedbyheatingleaddataillustratetholawofcoostantcomposition.
IIT
R
EE
AR
C
S
N
IA
IIT
100 = 75 '76qo
% of oxy*D = 20%
elements nitrogen and orygen combine to Produce peroxide qnd Nit/ogen penloide.
as many as 5 oxides of nitrogen, viz., Nitrous oxide, The masses of nitrogen and orygen which
combine with one another arc : -
Compound Nitrous Nitric Nitrogen Nitrog€n Nitrogen
oxide oxide trloxide t€traoxide pentoxide
(Nzo) (No) (N2()3) (N2O.) (N205)
Fixingthemassofnitrogenas14parts,the-masseso-fory^gcnin.thesehveoxidesareS'16'24'32alid'
l8'paitii"ipectinely.Theseirassesbearasimpleratioofl:2:3:4:5tooneanother'
PHOPORTIONS
- . l.'\ \\lf,l.l' t. Carbon is lowtd to form wo Ir\ \\ll'! l. I Two oxides of a cetl^in metal
' oxides, which contafu 42'9Vo and 2737o of carbon ,l
rcspectively. Sltow lhat these figtres illustrqte the lare
2
ol multinle prooorlions. (N.C.E'R'T')
0 2517 garns
grams of each oxide gave respectively
59!ut&L
ind 0'4526 grams of watcr Show lhat these results
Step | . To calculate thc Percentage cotnPosition R
establish the Law of MultiPle ProPorlions.
of corbon antl orygen in eqch ol the lwo oidcs
EE
Solution.
First oxide Second oxide Im calcutate the mass o[ orygen in eoch
AR
{ep
Carbon 42'g% 27 3% (Given) oxida.
C
I
C
RO9L EM F OR'PRACTICE
S
N
"
IA
1. T$o oxides of lead were separately reduced lo that lhes€ results arc iD accordancc with the law of
IIT
l. Crlculate the mass of lead combined wlth I g of 6. Calculate the mass€s oI Y which cambine with 1 I
o,rygen in each case which are 13.375I and 6.669I of X in each cas€ which arc 1.454 EarJd 435 g i.e.
ie. iD thc ratio of 2:1. in the ratio 1 : 3.
2. Cialculate the ma$les of copPer combined with 1.0 I 7. 22400 cc of N2 at STP weigh = 28 3- Calculate
of orygeo in each case which are 7.93 g and 3.97 8 the mass of nitrogeD. Then subtract from the
ie. in tbe ratio 2 : 1. mass ofoxidg ofnitrogeo to calculate the mass of
3. Calculatc the mass of Gygeo combined with o)rytco.
1.0I of nitrogen in each cas€ which are 0.571 I and E. Using (i), calculate the mass of lead Pres€nl in
1 .143 g, Le. in the ratio 1 : 2. htharge in (ii) and (iir. Then calculate the masses
4 Masses of metal tbat combine with 1.0 gofcxygen of qygen in allthe three cases which combine with
are 0.875 g and 1.773 8, the ra$o is 1:2. 1 g of lead. The ratio comes out to be 3 : 4 : 6
following examples
N
(l)
IA
2 32
H
they combine directly with each other lo form COv
as shown in Fig. 1.3.
4 H.2
As shown in the Fig., the masses of H and O
which combine with the lxed mass of S viz 32 parts
arc 2 ard 32 i-e. they are in the ratio 2 : 32 ot I | 76.
Whcn H and O combine directly to form
12 \16 HrO, the ratio of thcir combining masses is 2 : 16
,o
32
or1:8.
FIGURE 1.3. The two ratios are rclated to each other as
In CHo, 12 parts by mass of carbon combinc
1.1-,.,
16u
with 4 parts by urass of hydrogen. In HrO, 2 parts i.e. they are simple multiple of each other.
by mass of hydrogen combine with 16 parts by I,XAIIIPLE. Ammonia contain.r 82 35Vo ol
masscs oforygen. Thus the weight o{C and owhich nitrcgen and 17'65Vo of hydrogen. Water contains
combine wrth lxed mass of hydrogen (say 4 parts 88 90V. of orygen and 1l l0 % of hydrogen.
by mass) are 12 arld 32 i.e. lhey arc in the ratio Nitrogen tioxide contains 63 15 7o of orygen and,
12: 32 or 3 :8. 36' 85Vo of nitrogen. Show that lhese data illustrate
Now in CO2, 12 Parts bY mass of carbon the law of reciprocal proPoxions'
combine dircctly with 32 parts by mass of orygen
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SOiIE BASIC CONCEPTS IN CHEl"il|STRY 1127
,i2.35 .. lgolHcombinewithO =
1 g of H combine with N
17 .55 6 f#,
: 8.01 g
= 4.67 g ..Ratio oI the masses of N and O which
combine with lxed mass ( = 1 g) of H
:4 67:8.01=1:1.72
In N2C)3, ratio of masses of N and O which
combine with each other = 36.85 : 63.15
:1, : 7.71
Thus the two ratios are the same. Hence it
illustralcs the law of reciprocal proportions.
ROBLE M 3 FO R P,'RACiIII,G.E
"
1. Carbon dioride ml,tains2T .27 qo of carboo, carb-
97 .23 Eo of chlotine. Pree by calcularions, which
oD disulphide mntains 15 79 Va of carbol, and law is illustrated by these data.
sulphur dioxidc contaiDs 507, otsulphur. Arc these R
3. 61 8 g of A combine with 80 g of B. 30.9 g of A
figures in agreement with thc law of reciprocal
EE
combine with 106.5 g of C. B and C combine to
proportions ? [turs. Yesl form compound CB2. Aromic weights of C and B
AR
?P..ObLEMS
IIT
t. (15.79qo) c (27.21qa)
cs,'/\',/ \ co"
(84 2t%) S 12.1?%)
(soEa) so2 oo%)
(2 x 6 6 t) CBz (35.5 g)
1g -b with s = f+# = 5.33s
cwilt combire
1a 'ra
t g C will combine wi:-h O = 27.n- Mass of B mmbioingw h 1 gof A =
6i%- =
1.2e r
=2 6'7 I tt{ass of CcombiDingwith of A =
.. Ratio of masses of S and O which cambine wilh
1 g
#f = 3.45 S
fixed mass of carbon (viz I g) Ratio of masses of B and C combining with fixed
= 5 33 :2.67 massof A = I 29 : 3.45 = I : 2.67 = 3 : I
= 2:1. Ratio of masscs oIB and C combining direfifywith
Ratio of masscs ofS and O whicb combine directly each other
witheachother = 50: 50 = 1 : 1. l}lusthe tworatios = 13.2:35.5 = 1: 2.6.t = 3 : 3
are simple muldple of each other. Thus the two ratios arc samc.
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..dn
1.18. Gay Lussac'5 Law ol GaseouB volumes ,:',1
The ratio between the volumes of the rcac-
tants and the product in this reaction is simple, i.e.,
Gay Lussac invcstigated a large numbcr o[
I : 1 : 2. Hsnce it illustrates the Law of Combining
chemical rcactions occurring in gases. As a rcsult Volunus,
of his experiments, Gay Lussac found that there
cxists a definite relationship among the volumcs of (b) Conbination between hydngen dnd
thc gascous rcactants and thc Products. In 1808, hc oxygen. Tko volumes of hydrogen always combine
put forward a gcneralization knowr as ths Gay with one volumo of orygcn to produce two volumes
Lussac's Law of Combining Volumes.'fhis may bc of steam.
stated as follows : - 2llz + Oz 2HrO (steam)
2 !ol. I vol. 2 !ol.
-
Here also, the ratio betweetr the volumes of
thc reactants and the products is simplei.e.,2:7:2.
(c) Combination between nitrcgen and
hydtogen. Oncvolume of nitrogen a.[ways combines
with three volumes of hydrogen to form two
volumes of ammonia.
arnplcs:
N2 + 3H2 """""- 2NH,
1\ol. 3 !ol. 2 vol.
(a) Comhination between hydrogen ond
chlorine. ()te vollme of hydrogcn and one volumc
This reaction also indicates a simple ratio of
1 : 3 : 2 betwecn the volumes of the reactants and
of chlorine always combinc to form twovolumcs of
hydrochkrric acid gas. the products.
It R
may be emphasized here that the volume
H2 + Cl2 +
EE
zHCl
vol' used in the above reactions are exprcssed in similar
lol vol 2
AR
1 1
lurlrits i.e. , ml or lilres .
C
S
N
IA
IIT
fercnt ratios to fom more than one compotnd. For As a result of the researchcs made bv
etanple, sulphur combines with oxygen to fotm sul-
C
7- An atom is the smallest panicle lhat lakes since theysatisfactorily explain the laws ofchcmical
porl in a chemical reaction, lD other words, whole
IIT
into ener'
hypothesis by clcarly distinguishing betrveen thc
E= mcz.
C
laboratory reactions, atoms remqitt unaffected" i.e. cun lrrko part in a chomhal rcaction h muy or may
they can neither be creatcd nor destroyed, not be caphle of independant exlslence-
A molaule is lhz smsllas, Itarticl$ of an ebmenl or
1.23. Avogadro's HyPolhesis/ Law/Principle :r' ,, '
u compourul which is ctPable oI independmt eljst'
According to Gay-Lussac's Law ofgaseous ence.
volumes, ganes a/ways combine wi t one otother in Sincc thc smallest particlo ol a gas which can
a slnple ratio by volume- Bua according to Daltou's exist indepcndcntly is the moleculc and not thg
Atomic Theory, e/emenB combine with one anothet atom so thc volurne of a gas must be rclated to the
in a simple whole number atomic rslio to form com- numbcr r>f molcculcs (rather lhan atoms) prcsent
pounds . Beruelits, a Swedisb Chemist, tried to cor- in it. Hc thus put Iorwar d his hypothesis knorvn as
relate Dalton's Atomic Theory and Gay-Lussac's Avogadro's hypolhesis. This stal.es that
Law of gaseous volumes. He argued that while Equalvohtmx ol all gases undet simitu condilions
eleurcnts combine fu a s nple ratio by atoms, gdses
of tumperalwe and Pressurc cont{i3 equAl number
combinc in a simple ratio by volurnc, therc must be
of molecules.
some rclationship between the volume of a gas and
number ofatoms it contains. This led Berzelius 'lhis hypothcsis has hcen fountl 1o explain
the
to put forward his hypothesis callcd Berzelius clegantly allthc gascous reactions and is nowwide-
Hypothesis. It may be sl.ated as - ly recoguized as a law or a principlc known as
Avogadro's Law or Avogadro's principle.
E4ualwturn,s
Thc above rcaction bc(\a'cen hydrogcn and
oltet 2rEra.ts/8
chlorino can be cxplainod on ths basis oI
oJ dloitu.
Avogadro's Law as lollorvs :
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SOI\,,IE BASIC CONCEPTS IN CHEI\,4ISTFIY A-f
Hydrogen t Chlorinc __ Hydrogen
l vol l vol
chloride gas
2 vol.
vapourdensiryof a*^ = #Hffiff**
Mass of certain volume of thc sas at S-T.P
(By experiment)
Mass of same volume of H2 at S.T.P
fl moleculcs n molccules 2t moleculcs
_ Mass cf n molecules of the gas
(By Avogadro's Law)
Mass of n molecules of H,
j motecutc
I mobculc 1 molecule
Mass of 1 molecule of the gas
(By dividing throughour by Zr) Mass of 1 moleculc of H2(i.c. 2 atoms of H)
It implics that one molccule o[ hydrogcn Molecular mass
chloride gas is made up of] molecule ot hydrogen
0 089 g
)
S
Ofu ,
Taking thc cxample of oxygen, its atomicity
N
:
-
= 22.4x Mass of lL of the gas at S.Tp
IIT
as l bar and 0"C, STP will be takcn a! I atm and OCin thts book.
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1132 Pra rlc r :r's Net4 Course Chemistrglftfiffi
it, Alternatively, the mass of ar atom could have t - .
atomit mast anit (anu) is qad to
been calculated by wcighing a large sample oI the One
fi th o!
element and then dividing by the number of atoms E mt,o ol,,n dtom bI carbon-12 isow.
contained in it but unfortunately there was no
mcthod known to count the number of atoms. Thc Thus the atomic mass of hydrogen is 1.008
problcm was hnally solved by A,,ogad.ot am,u-while that of orygen is 15 9994 amu (or taken
irypothesis which states that "Equal volumcs of as16amu)'
diiferent gases under simi.lar conditions of Prior to 1961, two different standards were
tempcratur"e and pressurc contain equal numbcr of ' uscd for. expressing atomic masses wheu orygen
molccutcs." Thus ifcqual volumes oi two different was-used-as the reference Chemists on their scale
o[ (called chemical scale) assigned an exact value oI
oascs are taken undcr similar condil.ions
mass of orygen atoms as theyoccrr
i;;;;.. ;; o'...rt. ""J',r,., *"igi.J, ,r," inlbtothcaverage
nature' on the physical scale' the isotope ioo
rurio of rheir masscs *itt u" equat to ihc;;il;iil;
-rtt", ofin"ir.ingle molecules (because they con- *"t ^.tig"t!
exact value of 16' As naturally
1o consists of three isotopes (with
tained equal num[er of molecuies). For example, occurring.orygen
1? and 18)' the average value for
taking equat volumcs ofhydrogen and otyg"i, th.i, -11t iTb:f.16'
scal€ comes out to be 16 00214'
-"rrE ,i" always found in thi ."ti;; i;i;. iii. To rcmove this- duality' all atomic masses are- now
orygen on physical
means thal a moicculc of orygen it oii-"ti"*i.,
r
cxprcssed on the l2c scale' tzkitg mass of this
lhan a molecule of hydrogen. F;r',h.r";;;;
molcculc o[ hydrogcn con]tains two atoms o[ isotope as exactly 12. This sca]e k.called unilied
hyrlrogu, and one m6lecule of orygen contains two scale. On this.scale, the symbol 'u' is.used
instead
u,o- amu' though the symbol 'amu' is still used quite
-uto.-oi
,io,n."u1oryg.n, it -uybe intcrpie-ted iiu,un of
R
often in place of 'u' Thus now we better write are
of orygen iJ rO ti-". fr"uui"i tf,- -
EE
the atomic-mass of hydrogen 1 008 u and that of
hydrogen. Thus though ,rr" ,"4ri."..".'iiii" as
AR
orygen as 16 u'
aio-Jcould not be d-etermined but their relative
masscs could be determined. It follows that if the The atomic masses of the elements have been
C
itcomesouttobe15.88).,isfoundthatinanumberofcases,atomsofthe
IIT
For example, naturally occurriog [eon coil- Lastly, it may be pointed out that naturally
sists of three isotopes, the mass numbers of which occurring carbon contains three isotopes of carbon
and thsir fractional abundances are as follows : with atomic masses 12, 13 aod 14 u. It is the carb-
Isotop€ Fractional Abundance on-12 isotope that is taken as a reference on the
20Ne 0 9051 atomic mass scale.
2lNe 0 0027 The atomicmasses of a fewcommon elements
22N" 0.0922 taking carbon- 12 isotope as the reference are given
Averagc atomic mass of neon in Table 1.4.
= 20 x 0.9051+27 x 0.0027+22 x 0.0922
= 2A 779 tt
tAItLFl 1.4. Atomic masses ofsome corrmon elcments (taking C-12 = 12.000)
I .008
N
f'X \\ ll'l-ll. Use the dala given in the lollowing 1.25. Gram Alomic lrass
table to calculate the molar mass of naturully occut-
The alomic mass of an el ncnt expr*sal in grans
nnq argon.
is ctlled Gram atomic mass,
Isolope Isotopic molqr mass Abudatce
36A, 35 .96755 g mol-1 0'3!7Vo This amount of the element is also called onz
grum atom.
3EA, 37.96272 g nrol-1 0'0637o e.g. Atomic mass of orygen 16 amu :
eA, j9.9624 g mot-l 99.6NEo Gram atomic mass of oxygcn
(N.C.E.R-T) (or one gram atom of orygen) = lg g
, r ',:: i..ir ,r: i, .T::
Solutiot. Molar mass of Ar
= 35.96755 x 0.00337 + 37. 272 Molecular mass of a substance refers to the
x 0.00063 + 39.96924 x 0.99600 relative mass of its molecule and is defined in a
manner similar to the atomfug mass a5 follows :
= 39.948 g mol-r.
?ilu moluulu @.*s o! ti iubiuae (elencnr or
Note. Also see Problems 18 page 1/7 and 29 compouttd) is tk4.ii$nber d tit 6 thz molecub ol
page 7178 of C.B.S.E. PM.T. (Special) Problems lhc substarct tt hlolter lhan 1 112 th thc mass olan
given at the cnd of this unit for calculation of alom ol carbon-L2 isonpe.
average atomic mass.
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1lu Pradeep's
(t.022x 7O23 molscules of any gas at STP (i.c. 3rd Dellnition (in terms of volume), In case o!
standard tsmperature and prcssurs viz 0"C ar,d gases, t mok is deJinul fls tlur qmtu of fte gas
atmospheric pressure) must havs the same volume. whirh hu a volwrw of 22 4 litrcs dt STP
This volur^re has been expcrimentally found to be
22.4 litres at STP (0"C, 1 atm or '1 01 bar e.g. 1 Mole o[ oxygcn gas : 22 4 litrcs of
pressure) and is callcd molar volume* (bccausc oxfgen at STP
6.022 x molcculcs reprcsent onc mole o[ the
lO23 1 Mole of CO, gas : 22 4 litrcs of CO2 at STP
gas, as already di:cusscd).
REMEMBER
Keeping itr view the differcnt aspects dis-
cusscd abovc, a mole may be defined in any one of Iu C.GS, system,
the following three ways :
I g mole = Molerular mass expressed in grams
lst Dcfnition (tn tenns ofmass).;l nole ic.lefind = 6'022 x 1d3 molecules
as tlut omnmlolthe substarce vhich hasmosquol
to gmn aromb mosl iI tte subslalre b atotnie or In M,K.S. slstem,
grum molauhr nutss if thc subfiq!,cc is t olafurl 1 kg mole = Molecular mass expressed in kg
c.g. 1. Mole o[ carbon atoms : 12 g = 6 .O22 x 10x molecules
(. At.massof C = 12u) Mole Concept for Ionic Compounds. The for-
1 Mole of sodiurn atoms : 23 g
mula of an ionic compound does not reprcscnt a
( . At. mass of Na = 23 u) molecule of that compound but expresses only thc
1 Mole of oxygcn atoms = 16 g rclative ratio of their constituent ions. Howcver. the
(. At.massof O = 16u) [erm mole is applicable to thcse compounds also
1 Mole of orygen molecules : 32 g
R
with thc modification that the term'formula mass'
EE
( Mol mass of O, = l2 u) is used in placc of 'molecular mass' and lhe term
'formula unit'is used in placc of 'molecule'. Thus
AR
(,' Mol mass of COz = 44u) grams) or vhich cottains Avogadro's number
IA
"IE@WW'@N
S
N
IA
Recspitulatlon of trorloulas
IIT
1 I\,IOLE OF ATOMS
1YPE I. On the calcul tlon ofthe actusl I \ \\11'! i. -\ Calculate the number of
rn ss ofa sitrglc alom or a sitrgle trrolecule molecules present
(i) in 34 20 grams ol cane sugar
\\\i!lI L
Calculate the msss ol (i) an (c t2 H 22o t )
atom of silver (ii) a molecule ol cafuon dioxide.
: -liifin on" litre oI watet essuming thqt thc
Solution. (i) 1 mole of Ag atoms 10tJ g
density of wstet is I glcm].
( . Atomic mass of silvcr = 108 u)
(iii) in one drop of water having mass 0'05 g.
= 6 022 x 1023 atoms
Solution. (i) 1 mole of C,rHrrO 1 : 342 g
6.072 x lF atoms of silver have mass = 108 g
. . Mass of one atom of silver [ .' Molecular mass of cane sugar (C1rHrrO.,,)
lo8 = 12x72+22x7+ 11 x 16 = 342 amul
= 6.022xt0'J., = l'793 x lo-n g
= 6'022 x 104 molecules
(ii) 1 mole of CO, = zt4 g Now 142 g of cane sugar contain
6.022 x 1023 molecules
( . Molecular mass of Co,
. . 34 2 g of cane sugar will contain
=1x12+2x16=44u)
6'022 x rF
Thus, 6 022 x
= 6 OZ2 x 108 molecules
1023 molecules of CO, havc
= -"fi: rU'Z
mass = 44g = 6'022 x 1d2 molecules
. . L molccule of CC), has mass (ii) 1mole of watcr = l8g= 6 022x1e3
moleculcs R
44 44 x 1:0-23
:
EE
c Mass of 1 litre of water volume x density
6.022 x 1G3 6.On x 1=
= 1m0C
AR
1000
= 7.307 x lo-ts g
Nou 18 g o[ water contains = 6'022 x 7021
C
. 1000 g of watcr
IA
volumc = l8 cm3
'l-\ I'l! tl I. ( )n lhc crlculxlion of rrrnrl'cr .
. 1 molccule of HrO will havc volume
C
6.022 x, 7U5
IA
.'. 3929otHrSO4=:x392
1
-u." = 6"r;*-r*, x rF = 2.6s7 e.
AR
= 4 moles of HzSOr.
i.e. 22400 cm3 oIHz at STP have mass = 2 g
S
= ! x9
1
.'. 9g of aluminium .
. Mass of 1 atom of
" = ----4q--
Ag
6.022 x 702i
= 0.33 mole of Al
(v) l metric ton ofFe
1d kg : : ld g
= 1'793 x 10-22g
I mole ofFe = 56gofFe (ii ) Mass of one gram atom of N : At. mass
grams = 14.0 g
in .
(r)i) 2.5 moles of CI2 'l 5. Which of the following weighs most ?
IA
(i) 50 I of iroD
IIT
11, Calculate the mass of 1 molecule of- 16. The mass of 350 cm3 of a diaromic gas at 273 K at
(i) oxygen (ri) ammonia 2 atmospheres pressure is one gram. Calculate thc
mass ofone atom of the gas.
t \,i. (i) 5.314 x 10-23 g (ii) 2.t23 x 10-2r gI
12. (a) Calculate ihc volume occupied ar STP by [ \ns 2'657 x 10-23g]
(i) 16.0 g of orygeo (!i) 1.5 motes of orygen aDd 17. How many atoms and molecules ofphosphorus are
(iii) 6.022 x 104 molecules of carbon diodde preseDr in 124 g of phosphorus (p, ?
I r,,.. (i)
ll.20litres (ii) 33.60|itrcs (iri) 22"4 litrcsl I ru. 24.0Ettld! atoms and 6,022x1F DoleculesJ
13. (i) Ho\" many grams of H2S are conrained in 0.40 lt. What is the mass of a water molecule in gram ?
mole of H2S ? How maDy molecules are pres€nt in one drop of
L\ns 13.6 gl
purewaterwhich weighs 0.05 g.Ifthe same dropof
(ii) How many tram aroms of H and S are con-
wa tcr evaporates in one hour, calculate the numb€r
tained in 0.4O mole of H2S ?
ofmolecules leaving the liquid surfac€ p€r s€cond.
[,u,s 0.t I otoms ofH ond 0.4 g atoEs ofSl
(rii) Hotp many molecules of H2S are containcd in [ \r)\ 2.989 x lO-23 9,1.673 x l02r moleculcs
x 1017 molecutes/sec.l
and 4.647
0''!0 mole of H2s?[
rns.2.4t8Ex10P molctules] 19. What is rbe mass of carbon present in 0.5 mole of
(iv) How marry atoms of H and S are contained in K1 [Fe (CN)6] ?
lrn. 36 gl
0'40 mole of H2s ?[ 20. The cost of table salt (NaCl) and table
t,r 4.tl76xr0! atoms ofH sugar
and 2.4(BE x lF atoms ofsl
(cr2H22oll) is Rs. 2 per kg and Rs. 6 per kg
14. You are supplied with a gas contaiDiDg 0.32 g of respectively. C.alculate their msts per mole.
cxygen. Calculate the Dumber of moles aDd Dum- R [.\Is. Solt = 12 p, Sugsr = Rs. 2.OS p]
EE
ber ofmolecules present in it. 21. Chlorophyll, the green mtouring matter of planrs
AR
[.rrr..0.01 rnote, 6.022 x ldr molecules] responsible for photosynthesis, contains 2.68% of
15. The mass ofa litre oforygen atsrandard conditioDs magnesium by weighi. Calculate the number of
C
of temperature and pressure is 1.43 g and that ofa magnesium aroms in 2.0 g ofchlorophyll.
S
(i) How many molecules of each gas are there in 22. Ho,v much timEGiidli-iake to disrribure one
?
IIT
this volume [ADs.2.6EE x ld, moleculesl Avogadro's number ofwheat grains if 1010 grains
(ii) What is the mass in grams of a single molecule are distributed each s€cond ?
ofeachgas? [.rrrs.oz 5.320 x t0-,3gand I aD.. 1m,t93 ],rars approx.I
=
23. Calculate the total numb€r ofelectrons prescnt in
SO2 = 10'629 x 10-23 gl
I .4 I of nitrogen gas.
(rii) What are rhe molecular masscs of SO2 and
[ &rs.4.214 x ld3 electronst
02 resPectivel} ? [ \nr o: = 32.032 u and
SO2 = 63'D7 ul
ls. IL Oz or SO2 =
Zii
I
^ol
No. of molccules leavirg p", ,"" = Lffifff4
=fi"u'orxlosmolecules = 4 647 x 1017
19. I mol of K1 [Fb(cN)6] mntaim c = 6 I atom
= 2 688 x 1022 molecules
0 5 molof K1[Fe(CN)6] wilt coDtain C
Mass of 1 molecule of o.' = 1 43 ,, s =3 x1,28=369
2.688 x t0" - =6 x 0.5 gatom = 38atom
x 20. I mole of NaCl = 58 5 g
-- 5 32o 1O-B g
2 E57 .. Cost of NaClper mote =
1ft' x 58 sRs.
Mass of I molecule of So,
' = 2 688x10"..
=0ll7Re=11 1p=12p.
= 1.0629 x 1o-B g 1 mole of sugar (cl2Hz2o:fl) = 342 E
Gram Molecular mass of 02
= Mass of22 4 L at STP
.. Cost ofsugar per mote =
ffi x:lz Rs.
- 1.43 x 22 4 =32 O32g = Rs. 2.05p.
Molecular mass of Oz=32 O32 rt 21. 10Og chloropbyll contains Mg = 2 68 I
Similarly, molecular mass of So2 can be calculated .. 2 g chlorophyll will contaio Mg =ffi "
z
16. (i) Find the volume of the 8as at STP which is
= 0.0536 g
700 cm3
(ii) F-ind the mass of I mole ie. 22.4 litres of I mole of Mg=24g = 6'022 x 1oB atoms
R
8as at
EE
sry,Le. ffi =es -- o o536BME=9J4;fg xo 0536 atoms
AR
(ii) Calculate the mass of one molecule ie. = 1.345 x to2l atoms
C
(2) MolariBThe mobrit! of a solution isdqincd number of moles in the solution remains thc same,
as thc numbet oJ moles of the solute pfiEsent per we h ave
litre oJ thz sokrtion. It is representcd by the sym-
bol M. M,xV,=MrxV,
(3) Molallty. Tlu nolauty of a nfutim is dcfiictl This equation is called molarity equation.
ar tfu nunbcr ol molts of tlu nlute dissolvcd in
1 0OO E oI lhe solvcnr. It is Eprcsentcd by tlE slmhol,
For a balanced chemical equation involving
m.
,?
r moles of reacta.nt 1 and n, moles of reactant 2,
:r + .t, =1 amounts,
IA
IIT
ctooH
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1144
Pradeep's i
=;= 126
u, 12 38xVr = 010x10
0.r o
or V' = #L = rr-I*-l x tooOcms
1
Thus 250 cm3 of the solution contain oxalic to 50.0 cmJ in volumetic flask. Wat is the molaity
C
.. 1000 cm3 of the solution contain oxalic (b) How many grams of NuOH should be dis-
N
u"id =
$ x 1000 = 0.04geq 0.40
IIT
RO BL E M I FO R IPRACT,,l'6_iE
l. A "solution is prepared by dissoMog 18.25 g of
NaOH in distilled warer to givc
4. How many grams of barium chloride (BaCl, arc
2OO cm3 of the necded to prepare lm
solutioD. Calc-rJlate the molarity oftbe 6olution. cm3 of0.250 M Ilach sotu-
IArrs.2.2t Ml
tion ? s.20 gl I
2. How many moles and ho\ many grams ofsodium
5, How many moles and hof, many grams ofsodium
chloridc (NaCI) are pres€nt in 250 mI. ofa 0 50 M
chloride (NaCI) are prcsent in a50 cm3 of a 0.500 NaClsolution ?
M NaCl soluiion ? [,\rrs. 0 125 mol, 7.32 g]
6. A sample of NaNO3 weighiog 0.38I is placed m a
lArs.0.125 Eolg 7.312 gl 50 0 mL measuring flask. The llask rs then fillcd
3. CrnccntEted aqueous sulphuric acid k ggEa utttwater upto the mark on the neck- What is lhe
lI2SO1 by mass and has a density of 1.84 g cm-r. molarity of the solutron ? (NC.E.R.T.)
What volumc of the concentrated acid is required l-\,;.-:Im66'fri-
to make 5.0lire of 0.500 M H2SO4 sotution ? 7. lD g of NaOH is required
to the reaction. HowmaDy
[,rn,, 135 cm3; mi OI{ solurion shoutdbe
added for this requirement ? (N.(:.8.R.7:)
I 30.7 mt,l
R
EE
204
= 54.35 cm3 = iood'loo x 0 25 g
S
N
mole
'. Molarity ofthe given solurion 0.38I NaNO3 = = o.oo4s mol
\f 'or
=j?+"rooo=184M Moladty of Ihe solution !+3$ x ,0oo = o.oeo M.
-
Applying M1V1 = M2V2, 18.4 x Vt = 5 x 0 500 7. lmo mL of o. 150 M NaoH c{nrain NaoH
or Vl = 0.1361- = 136 cm3 = 0 150 mol = 0.150 x 40 : 6g
4. Molecular mass of BaCI2 = 137 + 7l = 208 u. re. 6 gin 0 150M MNaOHsolurion
= 1000 ml.
. 0 184 g in 0 150 M NaOH soturion
I.or 1000 cm3 of 1 M Baclz sol., mass of BaCl2
1000
necded = 208 g = -;- x 0.184 = 30.7 mL.
' l lamu(orlu)=#rhofmassotanaromofc-12=$g.ftaris*hyIirmuorluisarsocaflcdlAvogram.
l\o -
2 The number of molecules presenr in 1 cm3 of an idear tas at srp is calred t schmidt number.
rrsvatue = !+ftP = 2.6e x lore.
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1146
l1'arlaaS,'5 Neut Course Ch.-itt glfrm
tta ; b| i6: Y tix ii:rirvoirlED 6E-t6'diNfD::r:
::
.1 r\s ionic comPounds are not molecular, lhe terml[ormality, is used in plac€ of molaty to.exPress the
concenrratio[of thel t solltion. Fotmality is the number of formula weights present in one lifie of lhe sol tion.
No ot formura wcish'' = #*T*#;##H**
ii J Molarity of a solulion does not change wth temperature because it involves masses of the solute aod
Normalityand molarity changewith temperatule because they
solvent
involve
which d; not ohangewirh temperatuie.
volumes which change with tcmperature
:5. Standirrd solutior. A solution whose normality or molarity is koo$'n is callcd a standard solution
SOLUED EXAATPLES
C
S
IiXAI\{PLE l. (:okulate the perxentage com- Solutioo. Mol. mass ol (luSOo . 5 HrO
N
# =2xGa+q=X
= t2t x 100 = 5! 33%,
FORI :CiE';
l. "P..O?LEMS
Find the pcrc€ntage qjmposition of potassium
chloratc (KCIO3).
4A sample of clay is found ro have the formula
AJ2O3 . KzO . 6 SiO2. Calculate the perc€ntage of
I
rrr. K = 31 t47o, Cl = 2E 9aio, O = 39.taCol alumioa (Al2O3), F,orassium oxide (KzO) and sitica
2. C.alculate thc percenrage of (i) SO?- (x) H2O rn (sio2) in the sample. [ ,\n..Al2or=lt.3s%,
pure cq/stals ofMohr salt vtz.
K2O=16.90yo, SiO2 =64. 7 S%l
FeSO4. (NH4)2SO4. 6II2O.
5. Fe2(SOa)3 is used in water alld sewage treatmenr
I r". SOI- = 4t.9yEo,HzO = 21 ssEol to aid the remo\,ral of susp€nded impurities. Calcu-
3. Calculate the percentage ofwater of crtsrallisahon late the mass pcrcenlage of iron, sulphur and
in rhc samplc of washing soda, Na2CO; . l0 H2O. oxygcn in this compound. ,!NC,E.RA_-
l \F 62.94Ea1
[ \n\ Fe = 2t%, S = 24%,O = 48Col
vo
E"orFe=# xfio
IA
-- 28qo
2 (3?-+ 64)
- fio =
IIT
% of Sol... x 48.98%
4. Mol. mass of Al2O3 . K2O . 6 SiO2
r.ors=31# xrco=24%
= (2 x 2? + 3 x 16) =(2x39+16) +6 (2a+2x11) ..",o=o "-if6"t x too = 48o,0.
=102+94+360=556
When n = 1, Molecular Formula -- Empiri- the vatueJobtained for each element. This gives the
S
N
the salt.
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SOI\4E BASIC CONCEPTS IN CHEI.4ISTRY 't 149
Symhol Percentoge
otelements
Sodium Na 29.|t 23
,nir=r* r'26
-
Sulphur s 40.51 32
*ri'='* r.26
t2tu
1.R=',
',
o 3oift t, 1 .89
Oxygen 30.38 16 =I t.2ts-'' 3
ffi
N
T.J562 3
IIT
o r1J8
Oxygen 15. 18 16 = o elezs {ffi=,u* 8
Aluminium AI 10.50 27
lHo 039
=o.ss 039-' 1
Sulphur n 0.78 ^
s 24 96 32
\'{ =o 6.19 - '
a
l.\\l'll'l.ll R
L-The percentage composition of fenous ammonium sulphqte is 14.32Vo Fe2+;9.20Vo
EE
NHI p; a9 0% SO2n- and 27 57V. HrO. What is the empiicst fomuta oI the compound ?
AR
Percentxpe
the con6tituent ofconstituents or constrtuents =Eol:Effi ofcor!stituents
IA
IIT
,o lu2 o 2557
Iie2+ t4 32 56 = o.zss, o-.Nfr = |
eiSo 0 51I I
NH,* 920 18 = o srrr d.-T.l:t- = "
so?- 0.5104 .
49.0
*9 = o t'oo o-\91 - '
Hzo 2'7 5',7 l8 4d= r szz
r.532
o-.557 = 6
?ROE,'LEiltv{9 F-O,R
An inorganic salt on analysis gave the follo ing 2. An oxideofnitrogen gave the following percentage
perceDtage composition : composition:
Pb=62.6,N=4.4,O=29 N=25 94
What is empiric€lformula of rhe compound ? Also and O = 74.06
Dame the compound. (AI. mass Pb = 207, N = 14, Calculate ihe empirical formula of the compound.
o= 16). I rrr., PbN2o6.Pb(No3)t, r-ead Ditratel trr. N2O5l
I
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SOME BASIC CONCEPTS IN CHEMISTRY 1151
3. A sample ofsalt has rhc following perc€ntage com- Calculate the simplest formula. (At. mass of
posltlon: ME= ) [.\ns. MgSO. . 7H2O]
Fe=36 76;S = 21 11 and O=42 14
5. Calculate the empirical formula of told chloride
C-alculate the empirical formula
of the c.ompound. which conrains 35.1% ofchlorine. At. mass of Au
(At. mass Fe = 56, S = 32 and O = 16) = l9'7 - [ \n\ AuCI3l
[,\tr \. FeSO.] 6, Calculate theempirical formula ofa mineralhaving
4. A salt containing water of crystallizarion gave rhe the followrng composition :
4.
Con- Eoage Atomic Relaive no. of Simplert . Empirical Formula = Mgsoa . 7 H2O.
shtuenl nasslMoL cotlitti@nts Ratio 6.
m(us Vo
= Mo-l ,.ass Con- Voage MoL Relalive no. of const- Simplest
Mg 9.76 24 9 7624 = 0.407 1
tfihtenl nuus Vo Ratio
= M;1. moss
s 13.01 t3.ot12 I
Cao 48.0 56 48 0/56=0 857 9
=O 407 R
EE
o 21.o1 l6 .ov16 4 Pzos 41 3 142 41 31142 = O.291 3
=1626
AR
= 2.846
Empirical Formula -9 CaO.3 prO5. CaClr.
S
N
IA
IIT
:
analysis :
- Step l' Zo calculate the percent-
Na 14.28Vq S : 9. 92Vq H : 6.2Mo age of orygen. The given compound contains
Calculate the oxygen but its percentage is uot giveu. This can,
hydrous compound,. howevef, be calculated by subtracting the sum of
the compound are percentages of Na, S and H from 100 as shown
orygen as wakt of crystollizttion, what is the sfittctwe below :
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1152 Pradeay's Neut Coqrqe Chemistrg W
Sumof percentagc composition of Na,SandH = l4'?S+9'92+6'24=3O'4O
.'. Percetrtage of orygen = 100'00 - 30 ,10 = 69'60
Slcp 2. Tb calculate the empiical fotmula.
Element SyrEbol l'ercentage At mass RelBtive no. Simplest SiEplestwhole
ofelement ofelement ^
ol,lorrs. = _-:a
Percentaae
atomlc ratio no. atomic ratio
/\i- mx\s
a. q, o 31
Sulphur s 9.92 32 -ff=o tr 0.31 - ' 1
Hydrogen H 6.20 1
*= u^ # =ro 20
u'ru* o t
Orygen o 6960 16 = #?i =,0 t4
Hence the empirical formula of the com- Slep6. Tb calculate the numbet of molecules of
pound is NarSHrrOlo water of cryslallizattoz. Since all the H-atoms are
Step 3. 7o cdlculale the empirical fotmula present in thc form of H2O, 20 atoms of hydrogen
mass. Empirical forrnula mass of the compound would combine with 10 oxygen atoms to produce 10
(NqSlIr6O,a) molecu.les of HrO. Thus, the number of molecules
= 2x 23.0 + 1x x 1.0 + x 16'0 R
of water of crystallization present in the salt
EE
32.0 + 20 14
.taa NqSH26 O1a is 10.
-
AR
SIED 4. Tb calculate the value of 'n' Stfjp7 .'Io detetmine the st acture of the crystal'
mass
C
: Molecular 322
ofthe 14 oxygen atoms, 10 are present
= Ime Jarr. Out
,o= '
S
' E.piri";l for.ul'u -r.. in form of HrO. The remaining 4 must be a part of
N
Molecular formula = z x Empirical formula for this saltis Na5SOo and that of crystalline salt will
!r\ \ttlrl,l- 2. An oryanic substance containing carbon, hydrogen and orygen gave the following
pe rc entage c omposition.
C :40'687Vo;H=5'065Vo and O =54 228%
The vapour density of the compound is 59. Celculate the moleculor lormula of the compound'
Solution. Step l. Tb calculate the empiical formula of the compound-
oolf7 3.390 _
)
Carbon C 40.68',1 12 = z.tso 3.389 -'
5 985 5 .085
Hydrogeo H 5 .085 I = s.oas T3EEi =I) 3
sar? = z 3 389 _
2
Or(ygen o 54.m 16 zee TTtrq= I
?RACTICr-
l. A cr,stalline salt when heatcd becomes anhydrous 5. A chemicalcompound is found to have the follow-
and lo6es 51.2% of irs weighr. The anhydrous satt ing composition :
on analysis gave the following percentagc mmposi- C = 19.5'1Eo ,Fe = 15.2% ;N = 22 83 %;
tion:
K= 42 19%
ME = ?n OEo ;S = 26 66% arfi O = 53 31% Calculate the empirical formula of the compound.
Calculate the molecular formula of the anhydrous
salt and the cr)6talline salt. Molecular mass of the
R
What will be itsmolcc'ular formu la if lhe molecular
EE
mass of the compound is 368 ? Name the com-
anhydrous salt is 120. [,tDs MgSO..7H2OI pound and describe the action of hydrogen
AR
2. A mmpound cootaioing carbon, Irydrogen and perqide on it. [ \ns. K.I'e (CN)61
C
Calculate the molecular formula of the mmpound 8.45 mg of COz and 3.46 mg of HzO. The
IA
3. On analysis, a substanc! was found to have the experiment to be 88 amu. What is molecular for-
follo iDg perc€ntage composition : mula ? INC-U-T.) [ \,'s. c.H!o2l
K = 31.84, Cl = 28.98 and O = 39.18 . 7. A welding fuel gas contaios carbon and hydrogen
Cllculate its molecular formula if its molecular only. Buming a smau sample of it iD orygen gives
mass is 122.5. 3 389 carbon diuide, 0 690g of water and Do
[-rrr. KClO3l other products. A volume of 10.0 L (measured at
4. An organic liquid having carboD, hydrogeD, S.TP) of this \+plding gas is found to weigh 11.6g-
nitrogen and orygen was found ro contaiD C.alculate (i) empirical formula (ti) molar mass of
C=41.37%; H =5.757o; N = 16.09% and rhe tbe gas, and (rii) motecuhr formula. (N.C.E.R.T)
rest orygen- Calculate the molecular formulaof the
liquid if its VD. is 43.3. ['rrr.. (4 cH (i0 26 (iri) crHul
[,\)s. CaHrNO2l
2UCr t LEMs
1. Calculate the empirical formula of rhe aDhydrous . 120 g ofanhydrous salt contains ll2o
salt. It comes out to be MgSOa. E.E mass = 120.
Mol. mass = l2n. }Iencf,- molec'ular formula = =
ffi , rrr, = 126 g =
#motecules
MgSO1.
= 7 molecules.
As crystalline salt on becoming anhydrous los€s Henc€ mol. formula ofcrlstalline salt
51 .
2% by mass, this means
,ltl =MgSOr.7HzO.
8 g of anhydrous salt cootains HzO = 5l .2 g
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1154 Pralct l,'s Neut Coarse Chemistrgdffi)
trsually no direct method is used for finding the pErc€ntage of oxy8en in a compound. It is calculated by findiD8
the perc€nta8es of all elements except o,ry8en. Then %age of ory8en = 100 (Sum of Toages of all other
elements present in the compound).
-
18 g of water and ,14 g (or 22.4lilres at STP) of l.))t{\ I l'l-l,l 2. l hat mass oJ slaked lime would
carbon dioxide. be required to decompose completely 4 grams of
The qua-ntitative information conveyed by a qrnmonium chloide a.ad what would be the mass of
chemical equation helps in a number of calcula- eqch ptoduct ?
tions. The problems involving these calculations Solution. The equation reprcsenting the
may be classified into the following different types : decoffFoJtlon of NH.CI by slaked lime, i.e.,
(l) Mass-Mass Relationships i.e. mass of one Ca(OH), is,
of the reactants or products is given and the mass
of some other reactant or product is to be calcu-
ca (oH)2 + 2NH1CI CaCl,
latcd. 40+2 (1+16) 2 (r4+4+35 5) 40+2x35.5
=749 =1079 =1118
(2) Mass-Volume Relationship i.e. masV
volune of one of the reactants or products is given + 2NH3 + zH2O
and the volume/mass of the other is to be calcu- 2(r4+3x1) 2(2t1+16)
lated. =ug = a
(3) Volume-Volume Relationship i.e. volume of (i) calculate the mass of Co (OII), required
To
one of the reactatrts or the products is given and the to decompose 49 of NHoCl.
volume of the other is to be calculated.
From the above equation,
The gencral method ofcalculations for all the
problems of the above t,?es consists ofthe follow- 107 g of NH.CI are decomposed by 74 g of
ing steps : Ca (oH),
(i) Write dowtr the balanced chemical equa- . . 4 g of NH.CI will be decomposed by
tion. 'fa
(i) Write the relative number of moles or the R G, o= 2.76gof Ca(OH)2
EE
relative masses (gram atomic or molecular rnasses) Thus the mass of slaked lime required
AR
?2 4lrtres at STP below the formula in place of I 107 g of NH.CI when reacted with Ca(OH),
N
IA
(iv) Apply unitary method to make the re- . . 4 g of NH.CI when reacted with Ca(OH),
quired calculations.
Now we shall tale up a few solved examples will produce
to illustrate the different types of problems.
#"o=415gofcacl,
t'l l'[, L lnvohirlg ]lass-l\lass Rrlatiollship Hence the mass of CaCl, produced
233 g of BaSOo are produced from 142 g of Slep 2. To calculate lhe cosl of preparulion of
100 g of Hrfrom Zn.
C
NarSOa
: I
S
2 g of H, is produced from Zn 65
.'. 1,.74 g of it would be obtained from
N
would be the
.'. Cost of 2800 g of Fe = ,*_- x 2800
one ol these metals with H plO 4
'9hich
cheapest metal lo use ? Wich would be most ex' = Rs. 8.,10.
pensive ?
Thus Fe is the cheapest ald. Zn is the most
Solution. The various chemical reactions in- erpensive metal to use for the preparalion of H2.
volve n below :
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SOME BASIC CONCEPTS IN CHEMISTRY
1157
acid. 0.56r +
#(1 84 -r) = 0.e6
S
0.56.rx84+40x7.84-rl0x= x
IA
: 0.96 84
4.704 g.
or 47.04x - 40x = 80.64-73.60
IIT
"o-
x) c, = 0.872 (s
= i# - x) c
Thus the volumc of carbon dioxide
Actual residue obtained
= 25983 cm3.
_24 I'l\ \i\lPLI,I9. 1.0gof amimtre of cqrbonates
=5-1OOx5=1.68
of calcium and magnesium gave 240 cm3 of CO, at
.. 0'674x + 0'812 (5-r) : 3.6 STP Cslculste the percentage composition of the
or0 138x:0.216 mixture. R (West Bengal J.E.E.2003)
EE
or x = 3.339 Solution. Mass of mixture of carbonates of
Pb(NOr), in the mixure = 3 .33 g Ca and Mg taken = 1.0g
AR
t'.e.
. . Mass of MgCO. = (1
- r) g
S
= 1.67 E
N
-lYPIi ll. Inrolving Mrss-\'ol tnc l{clirliorrslrip The chemical equations involved are
IA
"""""'+ ...(,
, li\A\Il,l,l.l 8.
What volume of cafion dioide 40+ 12 +3x16
224tm cm!
measured at 27"C and 746.7 mm pressure $)ould be = 100 g at STP
obtained by treating 10. 0 g of pure mafile with dilute
hydrochloic acid ? (Aq. tension at 27'C is 26.7 mm).
MgCO: -----------r MgO + CO, ...(ii)
u+12+3x16
Solution. The chemical equation repre- =849
22400 cfi1
at STP
sentin[lf, E-reaction is -
Slfp l. Tocakulate the volume of COrevolved,
CaCO, +2HCl-..........' CaCt+HzO + COz
looc at STP from x g of CaCO ,.
:
""1T#" L00 g of CaCO, evolve COz at STP 22400 cm3
Step l. Tb calculate the volume of COrevolved . . x g of CaCO, will evolvc CO, at STP
from 10 g of CaCO, at STP.
From the chemical equation, : z?ff xr" '= z24xcm3
100 g of marble react to produce 22400 cm3 of
CO2 at STP Slep 2. Tb calculate the volume of COrevolved
orrgen at sTP
C
l
ustion oI 200 = ,'2[n = ul00 cm3 at STP
S
the volume of
N
IA
repre_
sent bustion of acctylene is = 4fi) cm3 at STp
9 FOP.- $T1{ I
rate of 25 paise per kilogram to mmplete ly
Deutral-
1. ize 7 kt of caustic poksh ?
[-r,1.. Cct olIICl = Rs, S.70, Coet ofH2SO.
= Rs. f,9fl
3 NO2 (8) + H2O (0- 2 HNO3 (4C) + No G) ? 5. Frxcess of AgNO3 solution nas added
to 2.2 E ot
commercial
water. The
ciloride was
collrmotr salt
[,a1". 30'27 91
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1/60 Pradeep's
-NaOH
12. How much matble of 96.5Vo purity would be re- obtained by allo ing 0. of metallic
quired lo prepare l0 litres of carbon dioxide at STP sdium to react with uater. s. 10.0 cElI
C
when thi marble is acted upon by dilute 20. FiDd out the volume of Cl2 at STP Produced by the
S
[ 1u(. 46.26 g]
N
hydrochloric acid ?
action ot 100 cm3 of 0.2 N HCI on exc€ss of
IA
1, 2 molcs of HNO3 are Produced from 3 moles of 40% HCI acid required = a suzs
#,
NO2 . 7 33 moles of HNO3 will be Produc€d from
= 11 40625 kg
NO,=]x7 33=10 995 moles. cost = 11.40625 x 50p = Rs 5 70P.
2, Fe2Or = 2Fe. 2KoH + HrSOn .. K2SO1 +2H2O
*'jr'uo'i ro 2x55 2x56kr 98 kg
' = ,2c Proc€ed as above to calculate the cost of 80%
.3. CaCo3 I' Hrsoo t 63590 * H2o + Co2 H2SO1.
1009 98g
50 g chalk will require Purc H2SOa = 49I 9. 2 KCIO3 +2KCl + 3Oz
+ HCt-
S
3 x 4x36.5s zz,roolFlisrp
IA
22400 mt
ar SIP
IIT
x Eq. mass
Normality
N
of KMnOn
= 0.5 x 49 = 24.5 gllitre
IA
Now, 1000 cm3 of the acid solution contain .'. 0 03 mole of HrCrOo will be oxidised by
IIT
24 5 g of pure HrSOo
2 x 9 03 KMnor
. . 500 cm3 of the acid solution will contain = o.o 12 mole of
5
g : Step 2. ?o calculate the volume o[ 0 05 M
- 'x
24'5
1000
l2'25gofPureHzSor
KMIO a solution .
Slep 2. Tb calculate the volume of H2liberute d
Now, 0'05 mole of KMnOo are contaiaed in
at STP
98 g of HrSO4 react to liberate 22400 cm3 of 1000 cm3 of the solution.
I
=tx0
AR
CL solution
N
=##x0.ools =30mL.
Quite ofteq one of t-he reactants is present in larger amount than the other
as required according to the
balanced equation The amount of th€ prcduct formEa u"i a"p.n*
up"" the reactant E{rich has reacted
completely. This reactantiscalledtherimiaingrtactantorrimiuo!Gg;.rlr"."r"t-,*rrr"ti.,.1*irr-"a
completely in the reaction is called exctss Eactant as tre excess;f
;s reacta is left unreacted.
SOLYED EXAMPLES
, I.l\..\IIPLE l.Zin c and hydrochloic acid react Thus, 1 mol ofzinc reacts with 2 moles of HCl.
accord.ing lo the reaction . . 0.30 mol of zinc will
Zn (s) + react with HCI
2 HCI (aq)
=7x0.30=0.60moI
ZnCl, (qq) + H2 @) But we have onlyO.52 mol of HCl. Hencc zinc
-
110.30 mol Zn qrc added to hydrcchloic acid cannot react completely and hence is not a limiting
c.ontaining 0. 52 mol of HCt, how many moles o[ reactant.
H, ure produced ? (N.C.E.R.T.) Again, 2 moles of HCI rcact with zinc
= lmol
Solution. The reaction is
. . 0 52 mol of HCI will. react with zinc
I
2;61 + zHCt (aq) =;x 0.52 = 0.26 mol
ZlCt, (aq) + H, (g)
-
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Ne.at Coursc Chent istrg
1164
As we have 0 30 mol of zinc, therefore, HCI Apply"g Gay Lussac's Law of Gaseous
. = 2 litres
S
at STP
02 left unreacted :29-23 8 : 5 2C
IIT
By mole concePt,
Mass of 22 4litresof COzatSTP
= Molecular mass in grams
Cahulale lhe mass ol each substance lutnd allet lhe
= L2+2x76 = 44 g
Wich one is orc limiting rcsclant ?
reaction.
Solution. The chemical equation repre- .'. Mass of 2litres of CO, at STP
sentin g thE-reaction is
= 16 '7'76 I
,r I Percentyicld' The actualyield ofa product inany reactioD is usually less than the rhcoretrcal yield (calculated
from the balanced chemical equation) because of certarn sidc reaitions taking place or less idealionditrons
than required. Hence we have percenr
feld = Th*re!!ffEh. x 100
:,i: l
R
Eudiometry' This isa method for finding the molecular formula ofa gaseous hydrocarbon. The apparatus
EE
rs
sho'sm in the Fig 1.6. The merhod iDvokes the following sreps:
AR
(i) A ktown volu me of the gaseous hydrocarbon is mued with an excrss (kno*n or un kno\xn volume) of orygen
or ak in the eudiometer over mercury.
C
(,i) Themixture is exploded by electric sPark and then cooled so that water
S
volume is negligible
IA
1r;
tcc I.*Ii xcc
\ 4./ ".
( i) KOH is introduc€d which absorbs CO2 and onty
unused 02 is left. Thus decrease in volumeon adding
tr(OH = Volume ot CO2 produed
Iues ofxand yare rhen calculated from the follow-
ing data :
= t*r)
I 4./
..
(!r) Volume of CO2 produced = r cc
(iii) Conrraction on explosion and c.oting
=1,.(,.+)]*-(-. )*
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r /66
r)radec j,'s Neut Caurse Chemiitryl&ElD
,
' once al
rrlr*rlujfirr.jr:r
egtlono
.r: : : I ri i: r: Inlr"jx+r+tn2'J:rtr:n:rtn
Q. What physical quantities arc r€presented by the follorying units and what are their most common Dsmes ?
(i) kg ms-2 (ii) kg m2 s-2 (iii) dm3
turs. (i) Force (ne$4oD) (ii) Work 0oule) (iii) Volume
(-). ]. Rewrite the following after required corrections :
(i) The letrBth ofa rod is l0 cms. (ii) The work done by a system is l0 Joules.
Ans. (i) The length of a rod is 10 cm (r is not uscd).
(r) The work done ry a system is l0 joules (small lettcr is used in placc ofcapital letter).
(.). -r Classify the follotf,ing substances into elements, compounds and Eixtures :
'
(i) Mitk (n) 22-@rat gold (iii) Iodil2d tsble salt (iy) Diamond (y) smokE (y0 steel (y4) Brass (vin) Dryice
(&) Mercury (.r) Air (E) Aerat d dritrl(s (!r) GluGe (ri.r) PetrovDiesevKer6ene oil (riv) StearD (rv) Cloud.
Ans. Elements (iv), (tt)
- (viii) , @r), (rir), @)
Compounds
- ( i), (v), (vi), (wi), (r), (r),
Mixtures- (,). (d), (11ii)
Ans. No, Iaw of constant compositioD is not true for all types of mmpounds. It is true only for the compounds
l2C and lac. When it forms
C
obtained from oDe isotope. For example, carbon exists in two common isotopes,
S
(.) I I L of a ges at S.T.P weighs I 97 g. What is the vaPour density of the gas ?
IIT
Ans. 22.4Lof tt]fvgas at S.TP willweigh = 197 x22 4= 44 l gia molecular mass =44 1. Hencevapour density
= 44.1/2 = 22 05.
(,) IWhy ltomic masses arc the average valucs ?
Ans. Most of the elements exist in different isotopes r.c. atoms with diiferent masses e.& Cl has iwo isotop€s with
mass numbers 35 aDd 37 existing in the ratio 3 : l Heoce average value is taken'
r.) r) Itryo bulbs Br and 82 ofequal caPacity contain 10g orygcn (or) and ozone (o3) resPectively which bulbwill
have great€r nurEber of O-atoms aud which will have Sreater nuEbcr ofmolecules ?
or x
l0 Smole = ]$ " e oz 104
g = molecules
r."' lvhy sre the etomic mosses of ulost of the elemerts fractionol ?
Ans. This is because atomic masses are the relative masses of atoms as compared with aD atom of C-12 isotope
taken as 12.
l-) ll llLite the formulae and nerDes of thrce clEurounds @ntaining ssme Frt€trhge.or,rp*ition of q H aDd o.
Atrs. Compounds with the same p€rceDtage compositioD of C, Il and O will have the same empirical formula. The
compounds with the cmpirical formula CH2O can b€
IICHO CH3COOH C5HI2O6
Formaldehydc Acetrc acid Glucqre
Ans, C-12
C
Ans CHrO.
N
Q.
Ans. mol dm-3.
IIT
CARRYING2oT3MARKS
\r( I l. 1, Chemistry can prove ro b€ a blessing or a curse depends upoD the us€s to which it is put. Crmmcnt.
l,! I -1.
sr( I.J 2. Briefly explain rhe difforence between precision and accuracy.
l0 l.(r
3. What do you m€n by 'sigDlficaDt figures, ?
4. Under what conditions the zerG in a oumber are sigDificaDt ?
5. After roundiDg ofl what $'ill be the value of
(i) t.z3s (ii) 1.22s ?
6, What does symbol SI siFiry ? Name the seven basic SI units ?
7. What do you understand by unit conversion factor? Hos, do€s it help to coovert height
in feet to
hcight in metres ?
r.. ls t. Define Element, Compound and Mixrure.
to 1.12.
9, Give examples ofhomogeneous mixturcs in different phlsical states (rwo each).
10. Give three main points of dilfereDce betwecn a compound and a miKure.
11. Classiry the following subsrances into elements, compounds aod mixtures.
Further separate the
mixtures into homogcneous or heterogeDeous :
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'1168 l'r,. tbt'y's Neut Course Chemistr:g mm
(r) air ( ) milk rrrr) graphite (iv) diamond (v) Sasoline (vi) mp water (vii) distilled water
(viii) qygen (rI) one rupee c
coin (x)22 at Eold (r) steel (ri) iroD (dii) sodium chloride
(.tiv) iodized table salt.
s(.c. I lJ. 12. dive one experiment invoMng a chemical reaction to prove that the law of conser%tion of mass is
t,) L llt true.
13. Copper oxidc obtained by heating copp€r carbonate or copper nitrate c.ontains copper and ory8en in
the same ratro by mass. Which law is illustrated by lhis observation ? State the law.
14. Nitrogen forms a number of oxrdes. Wrire their formulae and give their names. GMng apPropriate
calculations, exPlain the law that follows from it.
15. N and O combine with H to form NH3 and HzO and they combine with each other to form NO2-
Which law is illustrated? Explain bricfly.
15. Define Gay Lussac's law of Saseous volumes Explain witb one suitable e)(ample.
Srr. 1.10. 17. What are the postulates ofDalton's Atomic Theory ? How do the laws ofchemical combination follow
to L)) from it ?
lt. What are the postulates of Modern Atomic Theory?
se(. t :l- 19. Which isotope is used as a reference on ihc atomic scale ? What is one amu or one 'u' ?
1,, l.l7
20. Why atomic mass is an average value ? Frplain with a suitable examPle
Slj(. l.lti. 21, How N mole related to
(a) number of atoms/molecules
(b) mass of the substancE
(c) volumc of the Saseous substance ?
Empiiicat formula and Molecular formula. What is the relatioDship bet*€en them ?
IA
1o I -rJ
IIT
Scc. 1.7. 6. Define 'matter'. Briefly describ€ tbe phFical as well as chemical classification of matter.
lo l.tt.
Scc. 1.9. 7. DefiDe Element, Crmpound and Mixture. What arc homogeneous and heterogeneous mixtures ?
to 1.12. Give one example ofeach of the homogencous mifiure in the gaseous phas€, liquid phase and solid
phasc.
t. List ibe main points of difference berween a compound and a mixture.
Sec. 1.14. 9. State aDd explaiD the'[aw ofCoDservation of Mass'.
Scc. 1.15. 10. Defioe'Law of Consknt C-omposition or Definite Proponions'. Frplain with a suitable example.
Scc. 1,16. 11. State the Law of Multiple Proponions, Explain wirh two suitable examples.
scc. 1.17. 12. State and explain kw of Reciprocal ProponioDs.
Sec. l.lE. 13. What is Gay Lussac's I-aw of Gaseous Volumes ? Fjplain with two suitable emmples.
Sec. 1.20. 14. What are the main pclulates of DaltoD's Alomic Tbeory ? What were its limitations? Hotp has the
to 1.22. lheory been modi- fied ?
Sec. 1.23. 15. Define tbe follo$,ing :
to 1.27. (D Arom (ri) Molecule (rii) Aromic mass (iv) Gram atomic mass
(e) Molecular mass (vi) Gram molec1rlar mass.
Give suilable examples ilr cach case.
Define Avogadro's la$,. Thking a suirable example prove thai it is nor in conrradiction wirh Dalton,s
16.
Atomic Theory.
Scc, 1.2E. 77. Define Avogadro's Number' and.'Mole'. Whar is rhcir importance ?
Sec. 1.29. It. (a) Define the terms Solution, Solute and Sofvetrt.
(D) Define the differeDt methods used for expressing the concentration of a sotution.
Scc. I30. 19, Wbat are Errpirical and Molc@lar Formulae? Holp are they related io eaci other?
to 1.3.1.
R
EE
AR
C
S
N
IA
IIT
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EUt*l,NjE@,RM"
l. Averrgc Deyiatior. The simple$ way to epress precision is in tenns of average deviation. For this pu rPc€,
first the average of the different mssurements is calculated. TbeD the deviadon of each meaaurement from the
average is catqrlated, tahog all deviatioDs as positive. The average of these deviations is called average deviation.
2. Relatlve average d.drtion (r.o.d.). Precisioo is more ftequently exPressed in terrN of relative avcrage
deviation which is equal to average deviation dMded by average value of different measuremeDts.
ExsEplc. R
EE
Electronic charpe (esu) of individual maasurements Individual dzviation ftom the average
AR
4.81
IA
4 76 x 1o-lo 0 03 x 10-lo
IIT
Relarive error:ffiiiii#
ExrrEple. Experimentally determined value of electronic charge = 4 '19 x 10- to e.s.u-
Relatrve error _
- o or, to ]0x lm =_o 2.i
4.80 x l0-lu
1170
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SOME BASIC CONCEPTS IN CHEMISTBY 1171
hydrogen.
S
(ii) Oide fomarion or red.uction of the uide method. Calcl)late tbe mas of the metalwhich combines lvith
N
(iii) CHonde fomotion method. C.alculare rhe mass of the elcment which combines with or disPlaces 35 5
IIT
Molecular mass can be found from vaPour density (Mol. mass = 2 x VD) R
EE
(iv) Vobnle chloide rnethod. (FrcmeaDc,ur density measurements forelements formingvolatile chlorides)
C
If -r is he valency of the elemenl (M), then formula of its chloride will be MClr . Hence
N
IA
(ii) 160 has rhree significanr flgures while 160 0 Ans, Molality is the number of moles of the solute present
S
has four significant figures. Henc€ 160.0 repre- in I kg of the soh/enl whereas molarity is the numbcr
N
sen$ Sreater accuracy. of moles ofthe solu te present per lire oftbe solulion.
IA
Qf Which of the following has largest nuErber of Thusj molality invoi,rs only masses $,tich do Dot
IIT
Mol. wt.
N
electrons ir a kg' mole ofOt. the given sample ofwater = 9 + lO = 19g mol-l,
(West Bengal t.E.E- 2004) I'roblun 5. The average molar mass of a mixturc
Ans, One k8-mole (or simpty called one kilomole of metha!€ (cHa) and ethene (crH.) Present in the
(kmol) is the molecular mass of the substanc€ ratio of a : b is found to be 20'03 mol-!. If the ratio
expressed in kilograms.In CGS system, one gram were rcversedr whst vould be the molsr mass of the
mole ofa substanc€ contains Avogadro's number mixture ?
MKS s)6tem' one I
tains Avogadro's Molar mass of CH1 = 16I mol-
e is 6'022 x ld5 qHa = 2E t mot-1
Molar mass of
x tain 6'022 1G6
When they are Pres€nt in the ratio a . b, llrcit
molccules aDd hence 16 x 6 O22 x 1G6 avcragc molar mass
electrons.
B. PR()Rl.li]l\ ="
*'2ll*" = 203 mor-r (Giveo)
1 = 9{ r. 2 r,m.u.
=;bx100=r0%. Pruhlttn 9.Hov aary mol.cules rpproxlmately
C
l'nl'lut 7. Calculste the atomicity of Ecrcury doyou cxpect to bepr€entin (i) r small sugarcrystal
S
rDoleculcs from the following data : which weighs l0 mg (ii) one drop olwater with 0.05
N
cc volume ?
IA
to form an oxide. l)
(b) 500 EL of mercury vopour at S.T:B weigh =
4 465 E
= O.0r g = $mor- = 2.sz x10-5 mote
(c) Specinc heat ofmcrcury is 0 033. xrc-s) x (6.02 x loa)
= (2.s2
Solution. Calculatior of equivalent mass
= 1 7r x l0r9 molecules.
0 899of orygen combine with Hg = 10.0 g
'. 8 g of orygen will combine with Hg (ir) O 05 cc water = 0.05 I more
= $S
l0 = 2 ?8 x 1O-3 mole
=6T-x8=100t
= (2.78 x 10-1x (6.02 x 104) molecutes
.. Equivalent mass of mercury = 100
Cslculation of molar mass = l 6? x l02l molecules.
500 ,n L of mercury rapour at S.TP $righ = 4 . 465 t I'rohlun 10.9 7 x 1017 atoms of ircn ricigh as
. 22400 mL of me1'l(xry vapou r at S.TP wi weigh
Eluch as I cc of H2 at S,T,P What is the atomic mass of
iroE ?
=ffrzzeoot Solution. Mass of I cc of H2 at S.Tp
So[u1iqn. 100 parts by mass of the hydrated salt = *:#;#k= r eore x loroyears
contain 51 2 parts by mass of water. This means that
Gastric juice contains about 3-0Iof
C
Molccular mass of anhydrous MgS04 ,{tO mg of Al(OH)r arl needed to neutrelize all the HCI
IIT
Ilencc the formula of the hydrated salt is SolutioD. Normality is the number of millic-
7.nsot'ltllo. qui q) Perml-
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SOI\,4E BASIC CONCEPTS IN CHEMISTRY
1m
.. Meq of t N H2SO1 presenr origiDaly in 30 rn L Molar mass of miflure = 2 x v.D.
=30x1=30 =2x38.3=76.68mo1-l
Meq of O 2 N H2SOaiD 30 mL = 30 x 0.2 = 6
ExpressiDg all quantities in terms of moles, wc
'. Meq of H2SO4 required to be neutralized by should havc
NHr=36-6=24 r -r 100 l(n
.. Meq ofNH3 required to be passed = 24
4+-'q-=TF6
or92x+460O-46r=5521 8
(. Acid and base react with each other in
or 46x = 92A.8orx = 2O 1g
equivalent amounts)
But I mole of NFI, = 1g eq r.e. l0O0 Meq of
'. No. of moles of NO2 rn rhe mmure =
fl| =o ev
NH, = 22466 -1", 1U.r, I'tt.hlut 11 Naturally occtrring Doron consits
of lwo isolopes L'hose otomic weilhls arc lO Ol and
. ll OL The atomic weitht of natutal Borun is ll]. El.
24 Meq of NH3 - *frP , 24 = si1 .6 mL
Calculale the percealage of each isotope in natural
I'nhltm l,t. Chlorinc has two isotopes of atomic Boron. (M.L.N.R. A&4lu.had Ig94)
mass units 34.97 and 36 97, The relativc abuadances Solution. Supposc the percenlagc ol isotopc w h
of thess two isotopes are 0 TSSand0 245 respectively atom ic-wEilEf io.ot'= r
Find the aversge otoinic mass ofchlorine.
Then perceDtagc of isorop€ wirh alomic $,ctghr
(B.l.T. Roachi l99l) l1 0l = 100
Average atomlc mass .. -x
Average atomic weight
14.97 x 0 155 t36 9'1 x0.24s _ 10 01.r + (l0O -r) x 11.01
- =J5 46
100
I'nt,l r A gas mixture of 3 .O litres of propane
R 10 01 r + 1101 ll 0tr -.r
EE
1lO1
and buaane mplete combustior ot 2fC produced loo - IOO
l0 litres of CO2. Flnd out the coEpcitior of the gas
AR
..
N
6 4CO2 + 5H2O qa
= 20
IIT
or (E+17)x5 6=(E+a)x1 4
or 188=36 or F -20, and equivalent mass of HrPOo - U9f3!! = 03.
I'rohbn 21. C lculatc the mol rrity of rflater in
pure water. (Bihar C.E.C.E- 2000) Henc€ the ratio of masses ofH2SO4 and H3PO4
with 3 60
ofPotassi normality=01N
S
(N...E.R.T.)
IA
15N
In KBr, 32 9I of K are combined with nitro8etr as 14 (X)67' whst should be the ratio of
IIT
= 24
..
IA
4
4Y=x or ;= HeD"e +0.01 = 0 02 or x=0.539
or T k
i3 , tm = zs S*
O
Hencemolar ratio of HCOOH to (COOHtis4:1. Eo ofNaz1os =
I'robleu 4. Colculate the DuEber of oxalic acid
moleculcs in 100 ml of0 02 N oxalic acid solution. 70 of NaHCOT =o {, tm = eZ ot"
(Roortze 1991) % ofN%so4 = 100 - (26 5 + 42 O) = 31 5%
Solution. mlof0 02 N o,Glic acid solution
100
i rablen 6, Upou mixiug 45 0 ml ofO 25 M lead
=O 002g eq =0.OOlmole= 1o-3mole nitrrte solutioD teith 25 0 ml of 0 10 M chroElc sul-
phstc solution, percipitation of lesd sulphste takes
= 6 02 x 10m molecules. place. How many moles of lead sulPhatc ar€ forEed ?
Problefi 5. A2 Oesample ofa mixture contaitrhg Also calculote the molar concentration of th€ sp€cies
sodium carbonote, sodiuE bicarbonate atrd sodium sul' lefl behind in the llnel solutlon. Assum. that lead sul-
phate is gently heet d till the evolution ofCO2 ceascs. phate is complei.ly insotuble (AL wt of Pb = 2(, 2).
The volume ofCO2 at 750 BE Hg pressuie 8nd aa 29t K (I.I.T 199i)
is measured to be 123 9 IIrl. A 1 58 of the same satDPle Solution. 3Pb (NO3)2 + Cr2 (SOl)r
requires 150 ml of W10 HCI for coEPlete neutralizo- 3 moles I mole
tion. Calculate the pcrcent!8e comPo6itiou ofthe coltr' ........
(I.I.T, I 992\ 3Pb SO4 + 2 Cr (NO3)3
ponenLs of the mixture.
3 moles
SuPPoso Na2CO3 = x8, NaHCOT =)8'
45.0 ml of 0 25 M Pb (NO3)2 solution
Tllen Na2SO4 = 2 - (x + f) 8.
x
On heatlng only NaHCO3 will demmpose to give = ffi +5 mole of Pb (NO3)2
oz +
Mole fradioD of qH, =ffi=o oz
2 KI + H2SO4 + (O) + IqSO4 + H2O + I2
C
2 Na2SO3 + Na2SaO6+2NaI
N
=0 33
2Na2S2O3 + 2KI + 03 + H2SOa ....-..-
,l
IA
/ /
"r/,.r/ A mixture of 20 mL of CO, CHa and
IIT
N2 was bumt in excess of()2 resulting ir the reduction 02 + K2SOa + H2O + Na2S4O6 + 2 Nal
of 13 mL ofvolume. The residual gas was thcn treated 2 moles of NESz03 react wjth one mole of 03
with KOH solution to show a contraction of 14 mL in
volume. Calculate volume of CO, CHl and N2 in the No. of moles of NqS2O3 iD 40 ml of NES2O3
mixture. AII measurements are made at constart pres_ #
sure and tcmp€rature. 11
= m- x x to-3
e.I.T iggs) Jb;d x ao = 4 mote
Solution.
^-- = D7r1"n6 Slppose volume of CO = a mI_, .
CHo *, = crnl. Then 03 reacted (present) = 2 x l0-3 mole
a+b+c=zomt. (, Volume of O, =2x7O-3 x22.4L=0.0448L
The combustion reactions will be . Volume of 02= I-0.0448 =O9552L
1
CO+i()2-CO2 Weighr of 03 =2x10-3 x 48 = 0.096 g
Tbus, a rzl
of CO will produce CO2 = a mL = 1.4606 g
6 n L of CHa will pro du,ce COz = b mL .. % of 03 by weight = , rco = 6.s1r%
f#
Nz will remain
as suchi.e. = c mL No. of molecules in 2 x 10-3 mole of 03
As CO2 is absorbed by KOH, dccrease in volume
=2 x 1O-3 x J.022 x 7O23= 1.2044 \ rc21
on rreating with KoH will b€
No. ofphotoos required = 1.2044 x l02r
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1la2 !)ra tl,' r :,'. Net{ Co urse Chc m i strg fiffi
!'r,t r, n I't 1 2g mixture of Na2CO3 ord ,'.e, fICl left unreacted = 12 meq
K2CO3 was dissolved in va(er to form 100 cm3 of a HCI used up by MgO and Mg3N2
solution. 20 cm3 of this solutiotr required 40 cm3 of = 6O-12 = 48 meq = 48 millimoles
0.1 N HCI for neutralisation. Calculate the weight of Suppose in thc mixture, there are r millimoles of
NarCO, and K2CO3 in thc mixture. (Rootkee Dgn MgO andy millimoles of Mg3N2
Solution. Suppose weiSht of N%CO3 in the mix- Then 2r + 8), = 48
ture = rg: ot x+4Y=24
. Weight of IqCOr in the mixture = (1'2 x)g Further,
NHaCI + NaOII- NaCl .t H2O + NH3
46 + 17 .+ 148
Eq. wr. of N%CO3 Acid used up by NH3 = 10 6 = 4 meq.
-
?e-t',f48
'" ' ' " -oe . NII3 produced = 4meq = 4 millimoles
Eq. wl. or ryco3 = ; or NH4CI formed in reaction (ii) = 4 mjllimoles
No. ofgeq. ofNa2CO3 and IqCO3 in the mHturc Thiswill be formed from MgjN2 = 2 millimolesi a
x
- 53_l'2-,
_
69 l{ence ,r+4x2=24otx=16
40 cc of0 I N HCI coDtain g eq. ofHCl 2M8+02+2M8O
,1 1
3 Mg + N2........ Mg3N2
=-:-j-x40=4x10,
16 millimoles of MgO are obtained from Mg
Thus 20 cc of the mixture sol neutralize HCI R = 16 millimoles
EE
=4 x 10 'g eq
2 millimoles of Mg3N2 are obtaiDed from Mg
.
AR
* ,' 100
N
Eo
.
N
480
IIT
5' 112 cm3 of hydrogen gas at STP contain (c) 1g molecule (d)0 5gmolecule.
S
(c) 0
with 0 1 M HCI acid will
IIT
(d) xzv y
(a) 0 5Iatomof cu (6)0 6358ofcu (c) X Y2
(c) 0 25 moles of Cu atom
(LL X 1971 Is in
(d) 1g of Cu. 16. The largesl numbtr o[ moleculcs
9. 27 got N (at mass = 27) will react \\'ith oxYgen (a) 54 g of nitrogen Peroxide
equal to (b) 28 I of carbon dioxide
ltt) U B
(b)88 (d) 46I of ethylalmhol.
(c) 40 g (l) l0 s. '.rl.L \.R lr)lJ
III. 1 x 1010 g molecular weight of oxygen (c) all rhe orygen wi be consumed
C
IV 1x l0-18 g aromic weight of copper (d) all the ammonia wlll b€ consumed.
S
N
(a)II < I < III < IV (D)IV < III < II < I
IA
(c) II < III < I < IV (d) tII < tV < I < IL
27. lt)e number of nrolecules in 16 g of methane is
IIT
gas behaviour) is
(a) 1 (6) 0. I 24. 50 ml 10 N H2SO4 , 25 mt 12 N HCt aDd 40 mt
$.ot Jd) 0 001 5 N HNO3 were mixed togetherand the volumeof
t,tI L.\.R. 1991) lhe mixlure was madc lO0O ml by adding water.
22. 'Ilvo conEincrs p and e of equalvolume (1 litre The normality of the resultaDt soluiion will be :
each) contain 6g of02 and SO2 respectiirly at 3OO (a)1N (r) 2N
K and I atmosphere. Then (c)3N (d) 4N.
(a) No. of molecules in p is less than that in e
(6) No. of rhe molecules in e is less rhan that in p 'lte number of atoms in 4.25 g ot NII3 is ap_
(c) No. of molccules in p and e arE same proximately
(d) Eirher (4) or (6) tHo!.a nc.E.t:.t tset.\ 1x lF
(a) (\2xrG3
23. The maximum amount of BaSOa precipitated on (c) 4 x 104 @)6 x lofi.
mxing BaCI2 (0.5 M) wirh H2SO1 (1M) wilt mr_
respond to ' i, t l!,14 t tr'),!,
17. c ta. d 19, b 2ll. a 2t. c 22. b 23. a 24. b 25. c 26. c
27. b 2t. a 29. d
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1186
lrratleep's Neut Coursc thcmistrg lft[p
30. A molal solution B one tbat coEtaiDs 1 mole of a (a) 6.W x 1dl mohcutec of co,
solute in
(r) 22 . 4 L of CO2 at STP
(4) 1000 I of the sohrnt
(6) 0 44 g of CO2
(6) one litre of the solvent
(c) one litre ofthe sotudon (d) None of these. u.I.PM.Ii.R. 2000\
(d)22 4littes of the solution. (If
P CE E 7999) 3E. Number ofg of oxygeD in 32 28Na2SOa. l0H2O
31, A 1OO ml solution of O 1 N HCI was titrated with IS
(c) a.06 L
temperature ccntain the sa e number of
N
t,\ILlIS 2000) 44. The set of numerical coefficieflts that balances the
36. The number oI water molecules present in a drop equation
ofwater (volume0 0018 ml) at room temperature IqCrO4 + HCI IqCr2OT + KCI + H2O is
ls -
(a)6 023 x 101e (a; r.oel x tort (a) r,r,2,2,1 (b) 2,2, 1, 1, 1
1018 is
(a) gi$a (c) 2I) litres NH3, l0litrcs N2, 30 litrer tI2
(D) exa
C
(
IA
Number ofatoms in 558.6 g Fe (molar mass Fe 57. What volume of hydrogeD gas ar 273 K and I atm
=
be
presrure will
IIT
AJSWE
45. b 4.o 49. b 50. a 51. ./ 52. a 53. a 54. b
55. 56.
' '
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1/88 Neur Course Chemistrg
(c) 0.01,0.02 (d)o.o2,o t2 (b) 150 cc of N2 at ST?
t I 1- l: )t)t)l: (c) 50 cc ofSO2 at STP
60. The ma\imum number of molecules is present in
(d) 150 cc oI Oz at STP
.(oits t ottl, gass.TP (b) 5 L of N2 gas at s.TP
(e) 200 cc of NII3 at STP
(c) 0 5gofH2gas (d) l0gof02gas
66. A samplc ofphosphorus rrichloride (PCI3) contains
t( .l].\.1,. l)tl
l: )001\
1 4 mcrlcs of thc substancc. IIow many atoms are
61. 4 g of copper was dissolved in conctntrated nitric there is the sample ?
-fhe copper nitrate on strong heaiing
acid. Save 5g (a) 4 (6)s6
of its oxide. The equivalcnt wcight ofcopper is
(o)?3 (b)32 (c)12 (d)20 (c)8 431 x 108 (d)3 372 x tfa
( 'l l:2ttttlt (e)2.N9 x lfa iKtah l'l.l l:. 2u01)
1ft ouloog and tetir's law is 'M A gas mixture contains 50 helium and 50%
(a) metals (6) non-metals methane byvolume. What is tbe pcrcent byweiSht
(c) gaseous elements (rfsolid elements ofmeihane in the mixture ?
(a) le.e1% (b) 20 osva
(c) 50Vo (d)7s%
/480.$q. (turuln,tl. l'..ll. )0t)1
x \P
(a) 6.U2 (b) t2-04 x 1O22 116 mg compound on vaporisation ln a Victor
of a
Meyer's apparatus displaccs 44 8 ml of air
(c)1806x10P (d) 31.80 x 1028 measured at STP The molccular weight of the
(.1 t K.( .l.:.l.200J1 mmPound is
R
EE
64, One gram mole cf a gas at NTP occuPies 22 4 (a) 116 (b) 232
litrcs. This fact was derived from llfss (d) u.8
AR
65, Which of the following contains maximum number (a) 0.5 A/ 18 (6) 0.05 A
IIT
HINTS/EXPLANATION9 to
2. C-arbon particles (solid phasc) are disp€Bed iflto air
= :' x L |23 / l0.r mole'culcs
(gas€ous phas€).
9. 4N + 3Oz 2 NzOt = 2 77a x 1021 molecules
4x218 3x3zE - lelt
Atter removing 1021 moleculcs, molecules
10. Ag2Co3 Ag2O + CO2 1
2x1G+12+3x16 2x108+16
= (2.?38 - l) 1021
2t, NlVt + NrV, + NrV, = NoVo 45. Molarity of given Na2CO3 sol
lO x 50 + 12 x 25 + 5 x 40 =N4 x 265 r2S0.1000=0lM
C
1000 l
= 106
S
or N1 -lN
N
= 0 25 x 6 022 x IOImolecules
46. Ma.ss of 22.4 L of gas ar STp =fi "rr.o
= (1 + 3) x 0.2S x 6.022 x 1023 atoms
31. NtVt = N2V2 + N3V3 ie =30 g
0.1 x 100:0,2 x 30 + 0,25 Vl i.e. molccular mass of lhe gas = 30. Ileoc€ gas is
NO.
Ca3P2 + 6 HrO-* 3 Ca(OH)z + 2 pH3
47. Normali& ofoxalic acid soi.
u. Apprcx. atomic weight = 6.4,6pecific heat 3 1000 6
(DubnB aod Pe rifs law)
-250x 63 =oa\
35. l molofC6oIIjzz = 60 x 12 + 122 x1g =Bi2E 10x04=Vx0I or V=40mI
4t. l mol ofclecrrons weigh
= 6.O23 x lo23 molccules
36. 0 0018 ml fI2O = 0.0018I HzO = (9 r08 x 10-31) x (6.023 x 1023; kg
-( d= m1-l;
Ig or 9 108 x 10-31 x 6.023 x lF kg of elcctrons
1 mol II2O = 18 g - 6 023 x 1021 moiecules = 1 molofcleclrons
3E. 1 mol NESOa.IO H2O = 149 aroms of (O) . 1 kg of electrons
I
seg = 011 g ol lh€ compound. Hence = 106t mol
{$ ' l06gNarCOr=0l6el
C
As actual ycld is 50% of the expected value, NlI3 of molecules Lc. 6.02x 10?3. Ilcnce larger the
volume at S'ry greatcr is thc number ofmolecules.
formed = l0I- Nz reacted = 5 L, H2 reacted =
66. I mole of PCl3 contains 4 x 6.02 x 1023 atoms .
15L
1 4 moles will contain -3 31zx 1024 atoms.
'. Mixture will contain 10 L NH3, 25 L N2, 15 L H2.
67. Iiqual volumes contain equal number of moles.
57. 2 BC\ + 3H2 -* 28 +6HCl Heoce molar ratio of [Ie : CIIa = 1 : I . Ralio by
3x22.4L 2 x 10.t
*21 68 weight=4:16=1:4
-67 ?L . CH4 present by weight
)A = x rco = 8oEo.
U gC = limol = 2 mol = 2 x No atoms f
af at ST? will
6a- 22400 ml of be displaced by
569Fe = ffmol = l mol = No atoms =H+,22400s=5sg.
27 gN =;n,ol = I mol = N0atoms 69. 1 drop of water =
fr., = $.t
gag = (dn'o = 18 ml-l)
108
ffi mol = 1 mol = N0atoms
Mixture X will contain 0 02 mol Br- ions and lSgof water = A molecules
0 (}2 mol SOl- iotrs in 2 L solutioD. Hence I L of , Seno,"r= [,f = 9-.9I
n 6o1""u1",
mixture X willcontaid 0-01 mol Br- ard 0.01 mol
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SOI\,4E BASIC CONCEPTS IN CHEMISTRY
1/91
ADDITIONAL UESTIO,A,r.$
As rlci o n - Re a e o n Ty
=Li on s
ee p e e,u e
The folloylng n. While ans_wering
thes€ questionq you are r€quired to choose aDy one o
(d) If both Asscrtiotr and Rcssotr sre true o'd the Reason is a correct explaDstioD ofthe
AssertioD.
(r) If both Assertion and Rcoso' oDd true but Reasor is not a corr€ct expranatioo ofthe Assertion.
(c) IfAssertior is true but the Rlason is false.
(d) Ifthc Ass€rtion is fals. but the Rcssor is true.
(?) Ifboth Ass€rtion altd ReasoD orc false.
Ass€rtion Resson
Cinnabar is a chemic€l compound whereas brass is Cinnabar always contains 6.25 times as much
mercuryas
a mixture. sulphur by weight. Brass can be made with widely dif_
ferent ratios of copper and zinc,
A sio$e Cl2 atom has a mass enctly 12 amu and a Amole ofatoms o[any element has a mass in grams equal
mole of these atoms bas a mass of epcrly 12 grams. to its atomicweight.
R
Pure warer obtained from dlffereDt sourc€s such as Mass ofreactaDts and products duriDg
chemical or phlsi,
EE
river, e€ll, spring, s€a etc. alvays contains hydrogen cal change is always the same.
and Gygen in the mtio of I : 8 by mass.
AR
4. In a gaseous reaction, the ratio ofvolumes ofreac- Volume ot gas !s invers€ly proportional
lo ils moles ct
C
taDts and gas€{us producls is io agre€meDt with partrcular temperature aDd pressure.
S
The slandard unit for expressing the mass of atoms amu is also called as avogram.
IA
lll amu.
IIT
Both l06tofsodium carbonate and l2gofcarbon Bolh contain I g atom of carbon which contains
have same oumber of carboD atoms.
6.023 x 1023 carbon atoms.
Average aromic mass of boron is 10.3.
Boron has two isotopes B10 and Bl I who6e pcrcenrage
abundances are 19.6% and N.4Eo rcsrF ,tiflvely.
t. Atomlc mass of sodjum is 23.
AD arom of sodium is 23 rimes heavier than of rn"
$,n
mass ofcarbon atom 1cl2;.
True/Falee Statements
Wich of the followidg stdtements @e not true ? 5. Equalvolumes ofdifferent gases undc r srmilar con_
1. The zeros on the right of a decimal point are not olllons ot lemperature and pressure contarn equal
sigDificant. number ofatoms.
2. Petrol is a homogeneous mixlure of a Dumber of
6. Atom is not iDdestructible.
hydrocarbons.
3. Mass of re€dants is always equal to the mass of the 7. Empiricalformula represents the actualnumber of
products. atoms present in a molecule of the substance.
4, The volumcs of o(ygeo which combine wi$ a f ed &A balanced equation contains equal number of
volume of nitrogen in N2O , NO and NO2 bear a atoms of each elemenr on both sides of the equa_
simple ratio to one another. iion.
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1192
Prt:dt:a y's Neut Couvse Chemistrgffi[f)
picometrc = .........meire.
1
t. Accordiflg to S.I. a mole is that amount of thc
subslance which contains as many elemontary en-
4. A pure subsunce that contains only one kiDd o[ titics as there arc atoms in gxactly. ...---.kB of.....
atoms is callcd...... isotoPe.
The slrnbol 'u' uscd for exPressing atomic alld 9, 'fhc rcactant whlch reacts completcly aod decides
molecular masses represents............scale based oD lheamountof theProductiscalled.. ....''
-...........isotopc.
The law which state.s that a chemical comPound
10. The welghl of 1 x 1022 moleculos of
always contaios the samc elements comttined in a
CUSOa.5I{2Ois...--...... (l.I.T.1991',
hxcd ratio by mass is ca11ed.........
AJVSWERS
AR
C
l.a E'a
N
IA
TRUUFALSE S'TATEMENTS
IIT
r,4,5,7.
FILL IN THE BLANKS OUESTIONS
12 of constant
1- sionifrcant ficurcs 2. N m-2 or kg m-1 s-1 3. 10- 4' elemeot 5' uoified, C-12 6' law
."r"p*iirn oirr* of definite proponions 7' carbon, 12 t' 0 012, C-12 9' limiting reacknt
49 5.-,td7=t
,r.602x10" t+e.
[J N ITT
3taEes of lv,latter
.i.,.,':.i , l ril:i
Gaseous slate : Meas urable properties, the gas laws, ldeal gas .qu"rtion, kinetic molecular theory,
cieviation of real gases from ideal behaviour, liquefaction of gases, critical temperature and iis
importance.
Liquid state : Properties of liquids, qualitative description of vapour pressure, surlace tension.
viscositlt
R
EE
Solid state : Classification of solids based on different binding forces.
AR
General lntroductior
ture and pressure. For example, water which is a
C
In Unit I, Section III, we discussed the liquid under ordinary conditions of temperatnrc
S
compounds and mixtures. A passing reference 100'C and under one atmosphere or into ice (solid)
IIT
was made about the physical classification of by cooling to OoC under one atmosphere presstrre.
matter into solids, liquids and gases rvhich are A given substance can also exist simultaneous-
called the three states of matter. ly in all the three states under certain speciliccl
The aim of this unit is to discuss some impor- conditions of temperature and pressure. For cx-
tant aspects ofeach ofthe three states ofmatter one ample, water exists in all the three phases,viz. icc
by one. Howevcr, before we proceed [o discuss (solid), water (liquid) and water vapours (gas)
each of the states, let us try to review what we mean simultaneously at 0. 0L'C (273. 76 K) and 4. 58 mnr
by a solid, a liquid and a gas and in what important pressure.
characteristic properties the three states differ
from each other. Tlw temperatwe Nwhieh alt tlu lhree phases etu
tqethctis callod frlple pOint.
A suhstotce b said ta be soliditits meltingpoint
is above room temryroture under atmospheric The change of state is often accompanied by
pressare; c liquid if its mehing point is belov either absorption or evolution of heat. For example,
room temperctlute and bolling poinl is dbaw a solid can be converted into a liquid or a liquid into
room lemperdtare and c gas il its hoihng a gas by absorption of heat. This implies that a
point is below room temperalure under at- substance possesses least energy in the solid state
mospheric pressure. but maximum in the gaseous state.
It has becn found that in most cases, a given l'he essential points of difference between tho
substancc can be made to exist in any one of the three states of matter, namely, solids, liquids and
three states under different conditions of tempera- gases are given in Thble 2.1.
2fi
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i" ait.ttt's Neut Coutse I
TARLIi 2.1. Comparison of the characteristics ofa solid, a liquid and a gas
SOLID I,IQUID GAS
I. Molecules are closely packed Molecules are less closely packed. Molecules are sufficieDrly apart
from oDe another.
Mutual forces of attraction are Mutual forccs of attraction are Mutual forccs of attraction are al-
the strongest. weaker than those in solids. most negligible.
The density of solids is high. The density ofliquids is lower than Gases generally have low densrties.
that of solids but is much higher
than thai of gases.
The positions of molecules in tbe Molecules of a liquid have greater Molecules of e gas havc largc
crystal latdcc are fqed and heD@ freedom of movement. They have rotatory, vibraiory and translatory
solids do not have translatory or some tmDslatory and rotatory mo- motions-
rotatory motioD but only posess tiolls iD addition to tbe vibratory
vibratory motiou. motion.
Molecu les of a solid possess least Molecules of a liquid have higber Gas molecules are most energetic.
enerry. energies than those of solids.
Solids have borh a defiDire shape Liquids do not have definite Gases have neither delinite shapcs
and a deinite volume. shapes but have definire volumes. nor definite volumes.
7. Solids possess least compressibitity Uquids have slightly higher com- Gases prcrssess hrgh compressibiliry
and thermal expansion. pressibility and rhermal expansion and thermal expansion.
than thoso of solids.
R
EE
Qi) thennal energ possessed by the molecules
due to temperature which results into the move-
AR
apart.
S
ces and thermal etrergy. Hence molecules in a liq- volumes of liquids and solutions. These units are
uid exist together i.e. it is a condensed state of inter-related as follows :
matter but there is no rigidity. That is whytheyhave
no deFrnite shape. 1m3:1ddm3:
(ri) A solid melts on heatinq because on heat- 1ml:1cm3
ing, the thermal motion increase--s. llitre = 1d cm3 = 1dm3 :1O-3 m3
(ra) In both liquids and solid, their molecules (3) Measurrment of Pressure. Thc instru-
exist together i.e. both of them are con dansed state
.
rnv
barometer is
of the liquid.
As height of the
col tudy.
temperature of the gas. The aim of the present (ir) Mercury is non-volatile at room tempera-
section is, therefore, first to discuss the measure- ture. HeEce the vapour pressure due to mercury
ment of these properties of a gas and then to discuss R
vapours is negligible.
EE
some of the gas laws obeyed by the gases.
AR
,
S
N
IA
IIT
oo
dimensions of the container.
The SI unit ofvolume is m3. But this is too big
a unit. Hence the units commonly employed ari
cm3 or dm3. However the units ri and lities also FIGiURE 2.1. (a) Barometer (b) Ctos€d limb
contiuue to be used, genera-lly in expressing the manorneter (c) Open limb nEnometer.
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l'radc. t' " Net4 Course
2t4
The instrumeDt used for the measurement of However, the unit of pressure now commonly
used is 'bar'.
latm:1.01325bar
or 1bar : 0 987 atm
are : The SI utrit ofpressure is pasca.l (Pa) which is
, (i) Those in which the longer limb is closed dehned as the pressure exerted by a force of 1
(Fig. 2.1. b) nswtou on an area of 1 m2.
(it) ttrose in which the longer limb is open 1Pa = lNn-2 :7kgm-1s-2
(Ftg. 2.1. c)
Closed limb manometer is used only for gases The two units are related as
If density of mercury at room temp. As level in thc limb connected to the bulb is
S
= pgcIll " lower than that of the open limb, this means pres-
N
IA
= Axhxpgtam
.'. Weight of the mercury column
= Barometric pr€ssure
+ Difference of mercury levels
=(Axhxdxg +
= 74'3 cm 28'1 cm = 102'4 crn
where g is the acceleration due to gravity.
702'4
x
This weight ofthe mercury column is the [orce =|a'4 ^r^ -
1'o1325bar
acting on A cm2. Hence
76 --'-- 76
Force _Axhxpxg : 1 365 bar
Pressure (P) =
Area
The Kelvio scale of temperatues has FIGURE 2.2. Boyle's apparah.rs for study of effect of
emerged as a result of study on gases. It is possible pressue on the volume of air at room temp€rature
to cool a substatrce below 0'C arrd thus we can have
negative temperatures. But experimentally it is The following generalization was observed
found that it is not
possible to cool a gas below which is known as Boyle's law :
- 273 .15"C as aftq that the gas ceases to exist. Thus Temperatute remaining constanl, lhe volumc o! a
this is the lowest temperature that can be attained given mass of a gos k inverscl! proportional to its
and hence is taken as 0 K on the Kelvin scale. R
Pfessure.
EE
Negative Kelvin temperatures are as impossible as
negative volumes or negative lengths. Thus
Mathematically, Boyle's law may be stated as
AR
I
- 273.15'C : 0K V c( for a given mass of a gas at constaDt
C
i
or 0'C = 273.15 K
S
temperature
N
The first quantitative relationship between Thrs if P, and V, are the initial pressure and
the volume a.nd pressure of a gas was studied ex- rclume- of a gas and keeping the temperature cotr-
perimentally by Robert Boyle in 1662. The studies stanl, if pressure ; cl'anged io Pr, t-hen volume will
were made with air at room temperature. He used change to V, (say) such that acf,ording to Boyle,s law
mercury and a simple U-tube of the R?e shown in
Fig. 2.2. The pressure was increased by puttiug Pr vr = P2 v2 at co_Dstanl_t!T1"l",Yi
i
more mercury into the open limb. The volume of I
P P
o o o
FTGURE 2.4. Graphical verification of Boyle's law.
such
E
E
o
o
t
R
EE
We observe that if
constant temPerature,
AR
P
Graphical Verilication of Boyle's law. Ac-
S
-v or
P*1 PV=constant
IIT
Subcituting the corrcspouding values, ule have By applying Boyle's Law since temperature is
7fixlm=P2x180 constant,
amount of gas at 35"C aDd 1.2 bar pressure. The compress 5OO dm3 of air ar I bar ro 200 dm3 a r 30. ?
gas is transferred to anothcr vessel of volume 1g0
C
at
IA
3. PrVr = P2V2 Le. 1 .2 x 12O = Pz x lB0 After coonecring to bulb ofo 5 L capacity, volumc
or P2 = 0 8bar = (v + 0.s L)
r:e. V2 = (V + 0.5) L, Pz = 570 mm =5jO/ :,60 atm
4. Pressure at the surfac€ = 76 cm ofHg
APply PrV, = P2V2, calculare V
= 76 x 13 .6 cm of H2O = 10.3 m of H2O
-- Pressure al 10o/ll depth 7.Vr-25L,Pr=9x ld Nm-2 ;
= 100 + 10.3m = 1tO.3m v2= l 5 L,P2 = ?
ApplynS PrVr PzYz,
(At sufacc) (Ar tOO rn deprh)
Apply Pr V2. Calcutate P2. We get
Vr = P2
I-AW
on the effect of temPerature on the 6 c!
volume of gas at constant pressure were f[st
a
cafiied out bylhe French scientist, Jacques Charles 4 =
in 178? and then extended byJoscph Gay Lussac in =
1802. The following generalization was observed 2 l=
T
which is known as Charles' law : o
-273. t'
- r'oo o 1
+ TEMPERATURE lNoC 4
FIGUBE 2.6. Vdume oI a gas a'Iunction of temperature
or fall in lemperalure. ln centgrade.
Mathematically,
v,=vo +
fixt
= vo (+-L) (ry) world so far.
sam
where V, is the volume of the gas at l'C and V6 is its
are
volume at 0'C.
R
temperature axis at -27IC corresponditrg to zero
EE
The volume of a certain mass of a gas at any volume as shown in Fig. 2.7 below :
temperature can be calculated by the application of
AR
: * +# r!
S
Volume at 10oC ,o t
t
N
IA
z
= V, *
IIT
Votume at 1'C
* ul
f
J/o
volume at - r"c = vo - n3 o
20 vo
Volume at -20'C = Vo - 2J3
FIGURE temperature
273V^ (in oC constant
volume at -zil3'C= vo - td=o
This implies that a gas at - 273'C will have Absolute z*ro and Absolute Scale of
,"ro o. oo uo-Ir.", i.e., it will cease to exist. Below lbmperature,
this tive which
Tlu lowat
is m traced the
lemperalun
rate gas uPto
to luve Ttro
at constant pressure. In actual practice,
-27TC More careful experiments have shown that the
all gases liqueffbefore this temperature is reached'
absolute zero of temperature is -273.15'C' How-
The same conclusion can also be reached ever, for most of the purposes, tho approximate
tain mass
value of - 273'C is used.
re (along
a now scale of
h consist-
temp as its zero' This
scal; Kelvin scale or
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STATES OF MATTER 219
TK=fC+273
I
The relation V .( T implies that
where T xe{n I = ao*r,o, constant pressure.
[e.
and the scale - -Y
This 1' "t
,
vl v2
Tr = ,t at constart Pressure
R
EE
This form of Charles' law is very helpful in
solving numerical problems because knowing any
AR
2.e).
IA
IIT
TIJ
1
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2ho Neut Course Chemistrq
ture.
Experlmental Set up for the Study oflhrla-
tion of Pressurr wlth lbmpemturc at Constant
Mathematically, Yolume. This is shown in Fig. 2.11.
VARIABLE
(nl + t\ _-T
ir,= r. **)=r" \m -'0273
R
TEIUPERATURE
JACKET
EE
1r )
AR
PreT
IIT
= 21 '3E ml.
Givencond,itions Finalconditions
Vr = 20 ml vz: ?ml :
l'l \.\\ I I'l - I', At what tempersfiye centigade
^t;:75+2i73=238 K T2=35 +273:t08K witl the volume of a gas at 0'C double itse$ pressure
remaining constant ?
By applying Charles' Law Solution.
v2 20 Let the volume o[ the gas at 0"C : V ml
308 = 288
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STATES OF MATTER 2111
?RO7LEM? FOR:,fu:RAg, t
IIT
,[re:H I
1. 300 ml of orygen gas at heated to 10'C. 5. A steel taDk containing ah at atm pressure at l5"C is
15
What is the new volume -10'Care
if pressure remains con- provi&d with willyield at a presure of
a safety \,ahE that
stant ? Ii\rs.3',12.E mll 30 atm :rb 14tat mioimum temp€rature must the air be
2, 25 dm3 of ammonia at 283 K are heated uDtil its b€ated to blow the safety \ElrE ? [ \ns.303oc]
volumc is 30 dm3. -Ib what temperature must it 6. It is desired to iDcrease of the volume of a gas by
have been raised to accomplish the change ?
?i atitho]ul changiDg the pressure. To wbat
temperature, the gas must be heated if the iDitial
I,\lrs.39.6 KI temp€rature of the gas $ 27' ? [.\'rs EToCl
3. What will be the lolume of bydrogen when 3 litres 7. A gas cylindcr mrtaioing cooking gas can withstand
of it are cooled from 15'C to at constant a pressure of 14 9 atmospheres. The pressure
pressure ?
-73'C
[,{ns 2.0t33 litFsl gauge of the cylinder iDdicates 12 atmosphere at
4. What volume of air will b€ expelled from a vessel
n'C. D\e to sudden fire iD the building, the
containing,l0O cm3 at 7"C when it is he3red to 27'C temperaiure star6 rising. Atwhat temperature ths
at the same pressure ? I dr s . 2t.6 cm3] crti,lder will explode ? [ \ns 99.5PCl
5
Vr Vz
q=E'". cm3
4. 400 V2 This is the voluDe after expansion.
@TT7!R=@r+-n x^ . . Volume cxpElled
Boyle's law gives the effect of pressure on the Tt to T2 at constant pressure P2.
volume of a gas at constant temperature whereas uYz
Charles' law gives the effect of temperature on the '' Tr Tz
volume of a gas at constant pressure. However, it is
possible to derive an equation which gives the T.
simultaneous elfect of pressure and temperature or Y"= vx!lt
"
...(,,
on the volume of a gas. Substituting the value ofu ftom Eq. (i) in Eq.
The equorionvhbh givdstlu sir tlhn@us fia of (li), we have
pressure and tempontwe on tlv vohtme ol a gB is R P. V. T^
ur=
-I'i
EE
huwn as ideal gas eqwlionor eqtution oJ state{or
uruiflg4,,.
AR
...(rr,)
from Boyle's and Charlcs' law as explained below : T"i
't
S
frorn P, to P, and temperature from T, to T2 in the any hve variables are given and 6th is to be calcu-
following two steps as shown in Fig. 2.12. lated.
Another popular form of the ideal gas equa-
tion can be obtained as follows :
PxV
\ / INDIRECT WAY\ Eqn. (iii) implies that -i = Constant
STEP.I\ { \,STEP.2
= r (say)
The value of the constant K
dcpends only
I Pr,"r, I upon the amount ofthe gas taken.Ifn is the number
of moles of the gas taken, then it is found that
FIGURE 2.12. Change of slate assumed to Kdn
be taldng PlacP in two sleps
or K: nR -.(iy)
Step 1. Frst supPose that the volume of a given where R is a constant of proportionality and is
mass ofagas changes from V, tou when the pressure found to be independent of the nature of the gas
is changed from P, to P2 at constant temperature Tl. and depends only on the amount of the gas taken.
Then according to Boyle's Law, For 1 mole of any gas, the value of R is the same.
Hence R is called 'uniee$ql gas constant'.
P2xu=PtxVl
Substituting the value of K in eqn (iii), we get
Pr vr
or ,=
T ...(') PV
T=/tK
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STATES OF MATTEB 2113
lpv =;Rrl
This is the most commo! form ofthe ideal gas
-.(v)
":, + ...(viii)
1
Vct ixTxn changes when
C
chaoged. Thus,
S
1 ments involving
V=RxFxTxz
N
Nature and Yalues of the Gas Constant R. (iii) For ocpressing R in SI azi,r, put
From the gas equation, PV = n RX, we have
107ergs: l joule.
PxV = Pressure x Volume
R=--== * to'lor,"* degree-l mol-l
M.1". x 1b.pl""K HenceR: "foI
x :
ffi x 0-eogtnY ffi (Length)3 8'314joules degree-il mol-1
= E 314 JK-l mol-r
Moles x Degrees Moles x Degrees :
or directly taking P 101325 Nm-2 or Pa,
Force x Lensth Work
- Y = 0'0724m3, T = 2i73K
Moles x Degrees Moles x Degrees
weget R:8 314JK-l mol-r
= Work done p€r d€gree per mole or taking P = 101 325 kPa,
Thus R may be expressed in different units
depending upon the units of work.
!:22.4dm3,
Nurnerical Yalue of the Gas Constant (R) . T = 273 K
(i) At N.TP conditions, for I mok of the gas we get R = t'314kPadm3K-l mol-r
P: l atmosphere, Y =22'4 litres, (iv) To eqrex in terms of caloies, we know
't :2J3K n = l mole that 4 184joules = 1 calorie
Units of P Units
or Taking P = 1 bar so that
ofv
C
Y =22 7 dm3,
S
atmosph€re 0
^- lmolx273K or dlf
IA
or 0' 0821dm3atmK-lmol-1
IIT
Solution. Solutlon.
Given conditions Final conditions Let the volu-Ee of air in the tube be V ml.
? Given conditions New conditions
Pr = latm Pz= 1.5 atm Vr = Vml Vz = VmI
T| = 2:8+27 =!U K Tz= 273 + Ln P, = 760 mm = I atm. Pz = 3 atm.
450K ^ft :273+27 = 3O0K Tz: ?
Applying gas equation, we haJe
x By appllng gas equation, we have
t x V: 1.5 V2
3oo 450
VX1 VX3
.. 1xVx450 300 T2
'2- 3oox 1.5 ''' T2:300x3
.. Volume of the gas : V = $0K
.' A sealed tabe which cqn Thus the tcmperature above which the tube
wihsand a presure of 3 ofmosphere is ledwith ait will burst
f
at 2TC and 7& mm prcssurc. Find the Empetalurc = W-273
above which it will burst. : 627"C
FO
"RAfrL|,Ma
1. 50O ml ofnitrogen at 27o C are cooled ro
-5.C
the same pr6surs. Cflctllate the new volume.
ar 5. One litre flaskcontainiDgvapours of merhyl
EE
R
(Molmass 32) ata pressureof 1atm. and 25.C was
alc_ohol
I '
I Lr
446.7 ttrll evacuated till the nnal pressure was l0-3 mm.
AR
2. 400 ml of oxygen at 2fC were coolcd to _15.C How many molecules ofmethylalcoholwere left in
without the chaDge iD pressure. Calculate the mE_ the flask
C
?
1tuis.3.24 1 l0I5 moleculesl
traclion in volume. I s6.0 mU 6. 28.32 li!tres of chlorine w€re liberated at nornal
S
FORDIFF
4' Prvr Pzvz, 20 armx3oo L
-71 _= -T;Le- ----z,n*- I atmx60o L ot V2= 1.2O5 x 10-3 c.m3
22lO0 cm3 at S.TP. 6 .02 x
ot T2=29 3K = 1023 motecutes
appry
+=ryxV) , r=#. ,",* +=+"8
. 10-3 x tffD 760
Le. ----B- mn . 273K 0.964
=--7I- - 760
3otK ^ 7l o;; = -l-
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Ne.a, Couyse
2116
weigh : g'0625 t
.'. I bar
C
x227o0='t258
11
IIT
= 12 315 L atm.
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STATES OF MATTER
2117
l. C€lculate the number of moles ol hydrogen gas is then filled to a pressure of 735 mm at 31.C with
prescnt in 5@ cm3 of tbe gas taten at 3b0K ino i6O a gas of unkno\pn molecular mass aDd then
mm pressure. If this sample of hydrogeD is found rcweighed ; irs mass is 137.456 g. The flask is rhen
to have a mass equal to 4.09 x l0-2 g,calculatethe filled with waterandweighed again ;itsmass is now
molar mass of bydrogen. 1067.99. Assuming thar the gas is ideal, calculale
the molar mass ofthe gas.
I .1Ds2.03 x l0-2 Eole. 2.01 g mol-rl I EO.2S g mol_ll
2, 2.802 g of N2 gas is kepi in a lire flask at trC.
6. C-alculate the tempcrature of 4.0 moles of a gas
C.alqrlate the pressure exened ry thc gas. occupying 5 dm3 at 3.32 bar (R = 0.083 bar
[ \" '2.24 atEI dm3 K-r mol-l) .
N.C.E.R.T) I ,,.,s0 Kl
3. C-alculate the molar volume of 7. C.alculare the volume Gcupied by 8.8 g of CO2 at
a gas at ST?
[ .1ns22.4litrcrl 3i l'C and I bar pressure (R = 0.083 bar L
4. A 500 ml sample of a gas weighs 0.326 g ar 100"C K-lmol-r) (NC.E.R.T.) [ s.0s L)
and 0500 atm. What is the molecuhr mass of the t. 2 9 g ofa gas at 95oC occupied the same yolume as
8as ? [ 39.9 amul 0. 184 g of hydrogcn at l7.C at the same pressure.
5. A large flask fitted with a stop-cock is evacuared What is the molar mass of the gas ?
and weighed ; its mass is found to b€ 134.56j
E IL (N.C.E.R.T.) 1,rrrs40gmot-rl
-t I N -.- For-DtFFtc,uur ?RIrt:ava
t. L R
EE
Proceed as in sotued example This gives z = 0.036 mol
2.8(D 8 of N2 = 2.80218 mol. Mass of 0 036 otol of the gas
AR
#f,:? = 80.2s
1
s
Dke4 = 1mol, R = 0.0821 Latm K-l mol-l.
N
6. PV = aRT
IA
.. tut
dK 1.56x0.0821 x338
= P 745/760
The density of a gas is lound to
be 1.56 gllitre at 745 mn pressure ani 65.4. Catcu- = 44.2 u
lale the molecular mass of the gas.
_ _:
The density of a gas is 3.80 g
So_lution. Here we have d= 1.56glitrc-l L- ' at S:T.P. Cqlculste its density at 27,C and 70b
p=745mm=]9u,- torr pressure.
7fi
T : 65.C :65+273 = 338 K # a-
Solution. d = the same gas at two
R : 0.0821litre atm K-l mol-r different pressures aDd temperatures,
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2118
l'ralr ty's Neut Course
l. The density of a 8as is found to be 3.43 gniue at pressure is equal to 1 bar). I 29.3I Eol-rl
30OK aod l-.00 atm Pressure. Calculate the rDolar 3.
ma,ss of the ga.s.
I E4.5 g mol-ll
2. If the deosity of a gas at the sea level at 0'C is 1 '29
kg m-3, what will be its molar mass (Assume that
R
EE
2.
C
''.::!:!':!:::!:
S
'
IA
IIT
partial pressures :
Plrltospxem
Fig.2.14. =f(nl+xB+rlc+...)
S
r.\ \\tpLD 1. 38.U) ml of moist niiogen gas By applying the general gas equation :
were collected at 27C and 746.5 mm pressure. Cal- 7&xVz _ Tm x38
culale the volume of the gas at 0'C aad 7& mm
pressure. (Aq. tension at 2TC is 265 mm).
273 300
-. 'lm xS
Solutlon, :. Yr= -
3m.- * fr=22.rc^t
273
Given condilions Fhal conditions Volume of nitrogcn at ffC and 760 mm pres-
Vr : 38.0 ml Vz = ?ml sure : 32 .76 ml.
6y,q11p1 ,11 2. 25012I of nitrugen mointained, at
P t=746.5 -26.5:7m an Pz = 760 mm
720 mm pressare and j80 ml of orygen maintained
^ft=27 +273 =300K Tz= 0 + 2i73 at 6Y) mm Wssure arc put trythet in one litre flask.
IIthe temepmture is kcpt constanq what will be the
=Tl3K
fnd pressane of the minwe ?
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Neut Course Ch.mistrq
2120
or Pz=
7m x 250
= 180 mm
: 750-736.7 : 13'3 mm
1000
Altemaliveb, ifp is the vapour pressure of
Thus thc partial pressure due to nitrogen
(Pu) = 180 mm.
water at 15oC, then take P, = (750 - p) mm. Sub-
stituting in the equation
Step 2. To calculate the pattial pressure o[
oxySen
P. V. _i_:,
__t_: =
P" V"
we get
Given conditions Final conditions It 12
Vr = 380 ml Vz = 1000 ml
760Z_9t9 _ (750 -?).x 1000.
Solve torp.
Pr = 650 mm Pz: ? mrn
R 2:t3 248
t. A 2-L .lask contains 1 6 g of
EE
Applying Boyle's Law (since the temPetature
methaw and 0'5 g oI hydrogcn at 2TC. Calculate
AR
remains consta:rt)
x the poftial pressarc of each *as in the mintre and
1000 P2 = 380x650
C
380 x 650
= 247 mm Solutloo. 1.6pCH, = 19lnote = 0'1mole.
N
P2
1000 Ib
IA
= 247 mm. RT
Step 3. Tcr calculate the fnal prcssure of the =ncnlxT
gaseous miiule, x
If P is the final pressure of the gaseous mix- _01x0 0j821 300
= 1.23atm
ture, then accordi-og to Dalton's Law of Partial
Pressures, P=Pn, + Po, = 180 + 247 = 427 mm.
t
0.5sH, = f -ot=0 25 mote
t,xel,tt'l,E-r.A$venmassof a gas occupies
919.0 ml in dry sture 4t STP The same moss when
Pafiial pressure of Hz @uz) = rr, , Y
collected over v,latet 4t 15"C ond 750 mm pressure
occupies one litre volume. Cakulate lhe vaPour Prcs'
0.25 x 0 0821 x300
sure ol water at 15oC.
2
= 3'079 atm
s-slcEea-
S|ap l. Tb calculate the pressure of the dry gat Total pressure = Pcto+ Pu,
at 15"C and 750 mm pressure using the qas eEtation'
Given conditions at STP Final conditions = L'23 + 3'079 = 4 31atm
Vr : 919 ml Vz : 1000 ml l1\.\\lP 3.A gaseous mirtwe contains
g Nr, 44 g CO, and 16 g CHa- The total presswe
Pr : 760 mm Pz =? (DrY state)
56
of the mi*ure is 720 mm Hg Wat is the paftial
Tt =273 K. Tz=n3 +L5 =288K pressureofC,?
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SIAIES OF MATTER 2121
1. 2C0 ml of hydrogen and 250 ml of nitrogen each 4. What will be the pressure exerted by a mixture of
mcasurcd at l5'C and 760 mm pressure are pur 3 2 g of merhane and 4.4 E of carbon dioxide
rogether in a 500 ml flask. What will be the final contained iD a 9 dm3 flask at 27'C ? (N.C.E.R.T.)
pressure of the mixture at l5'C? [ \r\.6E4mm]
2. 400 ml of N2 at 700 mm and 300 ml of H2 gas
gas
lArr O.tZ atml
5. Wbat will be rhe pressure of the gas mixture when
at 800 mrn were iotroduced into a vesscl of 2 litres 0.5 L ofH2 at 0.8 bar and 2 0 L ofoxygen ar 0.7
at the saore tcDlperature. C-alculatc thc final pres-
bar are introduc€d in a I L vess€l at 27'C
surc of lhc gas mixture. I 260 mml (NC.E.R.1:.) [,$s.0 4 + l 4 = 1.E bsrl
?
orygen at 10O mm pressure rcspeclively are con- vess€iof l dm3at 27'C. Calculatc the totalpressure
nected to eacb othcr through a valve. What rvill be of the mixturc (R = 0 083 bar dm3 K-l mot-1)
the linal pressurc ofthc gasecus mixture assuming (N.c.E_R.7.)
lhat temp€raturc remains coDstant ? R
7. A minure of trydrcgen and oxyten at one barpres-
EE
[,\,.. Prrz = 32L43 mm. Po2 = 57.14 mEL sure contains 20% by urcight of trydrogen. Calcu late
the panial pressurc of trydrogen. (N.C.E.R.T)
AR
i.e. 2OO x '160 = P2 x 500 r|a p*, = 304 mrn 0.0821 dm3 atm K-1 mol-r x 300 K
9 dm3
For calculatioo of parlial prcssure of N2,
=0 55atm
Pr'V,' = Pr'17r' Pco.
rc. 76O x O = Pz' x 5N i.e. pN2 = 380 mm
14 4 \ 0 0821 dm3 atm K-l mol-l x 300 K
= (* ")
Finalprcssure of thc mixture ------ , dm3-
= 304 + 380 - 684 mm -O 27 atfi
3. Finalvolume = 15L+ 2.OL=3 5L pror.,=055+O27
For partial prcssure ofH2, PtVt = P"V2
= 0.82 atm
i.e.75O x 7.5 =Pzx3 5 5. Simriar to Problcm I and Problem 2.
orpHz = (750 x 1.5)/3 5 = 321 43mn nH"
7.Pur= i;!r- OxP
For partial pressure of Oz, Pt'V1, : pz,V2,
i.e. IOO x2 = P2' x 3.5 20a'/2
= fri7TT@i732 x 1 ba.
or poz = (100 x 2) / ?.5 = 57 .14 mm
10
' l',ni.,o," = 321 43 + 57 14 mm = 3?8 57 mm = raE= = 0.8 b".
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Net( Course
R
Ratc of diffusion f gas 2 (rr1 = 2
EE
o
t
lf d, d, are their resPoctive densities or
AR
ar,d
Ml and M2 are their respective molecular masses,
q
For two gases having densities dr and d, and
C
then
S
u, dt
=
IIT
fl d2
f2 dl Thus volumes of two gases effusedldifrused in
the sdme time (hrough the same oifice) under
Here the term'Rate of effusion diffusion' im- similur conditions of temPemture and pressure are
plies as under : inversely proportional to the squorc rools of theit
densities-
Rate of effusiory'diffusion
(iii) Comporison of times taken fot elfusionldif'
_ Volume of the gas effrxed/diffused fusion of the sarne volume ol lwo dfurenl gases.
- Time taken
Suppose r, is the time taken for the gas 1 for dif-
The law may be modified for different types
fusion of volume u and,2 is the time taken for gas 2
of calculations as follows :
for diffusion of the same volume u under same
conditions of temperature and Pressure and
vapour dersities.
As mol. mass
also write l
:2 x vapour density, we can
through the same orifice. Then
r., u/1, t, tl
h v/tz lr
dz
dr
rB
u/20
u
I -ffi-
/1O
q moniwn chloride will first aryea,
Solution.
*=ffi= \/
? (N.C.E.R.T)
By Graham's law of diffusion
1,' ={zTtr
or a= v80 = 1.465.
Thus NH, travels 1.465 timesfaster thanHCl.
or MB = 20 g mol-l
In other words, NH, will travel 1.465 cm in the
- 27 ml oI a cettain gas difuse in same time in which HCI travels 1 cm.
thes ml of chloine under the sunte Length o[ rhe rube = 200 cm.
cond,itions. Cakulale the molecular mass of lhe gas.
.'.Distance travelled in the tube bv
If , is the time taken for diffusion 1 465
of each gas, theu by Graham's law of diffusion NH: = x :
t.qfS + r 200 ll8'9cm
R
EE
rx ln/t 7t Thus NH.CI will lirsr appear at a distance of
AR
?.RO.BLEM3 FOR
N
IA
1. Calculate the molar massofaD unknotrn gaswhrch What are thc relative rates ofdiffusion ofthese two
IIT
dimrs€s 1 117 times faster than o(ygen gas through molecules under ideal conditioDs ?
the same aperture utrder thc same conditions of
temperature and pressure. Itrr. 0 9957 : 1 0]
4. 50 mlof hydrogen takes 10 minures to diffuses our
[;\ns. 25 65 g mol-l] of a vessel. How long will 40 ml of orygen take to
2.1f 25 ml of CO2 diffuses out of a vessel in 75 diffusa out under similar conditions ?
seconds, wbat volume of SO2 would diffuse out in Itu.32minutes1
the same time under the same conditions ? 5. A small quantiry of gaseous NH3 and HBr are
ttrs. 20 73 EU in-lroduced simulraneously tnto rhe oppGi[e ends
3. Uranium isotopes haw been separated by raking ot an op€n Iube which is one metre long. C_alculate
advantage of the differcnr rates of diftusion ofthi the distance ofthe white solid NH4B[ formed from
two fo-rms of u ranium hexafluoride, one contaming the aDd which was used to introduc€ NH3.
U-238 isotope and the other containing U_235:
I rrrs 6t 5t cm]
H lN rS FoRrlFFtcuLr ?RIrlLEv,I
1.rx-
,o, lE- 1111=\fF*
2' \ \/tl
12 v2/12
u*=nfiU=zs.65gmor
or r
- ti+=tE
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Neut Course
5t
'#HB='ffi or
or
fr="
l=32min.
5. Similar to solved examPle 3.
ffiB# =',/$=o*,,,;
For morc numericals, see .c.B.s.E. (PM.T.) and I.I.T. (Maitrs)', at the end of this unit. Problems 11
and L2, page 2160 and Problems 10, 13 at'd 15, page 2'165,66'
:I volume coemcient (au). Al constaot pressure, the incre3se in volume of a 8as P€r degrce rise of temPerature
v, - \'o
per cc of the gas at 0"C is called the volumQ c.reflicicnt of the Sas Mathematically, %= -I5 x r
Vo = volume of thc 8as at 0'C R
EE
Vr = volumc of thc gas at r'C
AR
I PEssure coeflicient (ap). -At constant volumg, the incrsase in the pressure of a 8as per degree
S
temperature divided by its pressure at 0'C is called pressure cocfficient of the Sas Mathematically
N
IA
".=H
IIT
(vi) The pressure exe,led on the walts of lhe aretitting the wall. they will exert some significant
push or an outward force on the wall. The force
C
(ii) The molecules are supposed to be perfectly inflation of a rubber balloon or a cvcle tube when
IA
elaslic hard spheres so lhat no enc,W is u,lasted, when more and more air is pumped into ii.
IIT
the molecules collide with one another o ith the Postulate (vii) statcs that the collisions are per-
w,alls oI the vessel. The energ) may, howeve; be
lectly elastic. If it were not so, the lorces of friction
transferred from some molecules to the olher on would havc slowcd down the molecules during every
collision.
collision. Ultimately, the gas should have scttlea down
(viii) Since the molecules are moving with dif-
-
Jerent velocitie!, they possess different kiiaic enir-
after somc time. Since this, in fact, does not happer!
the posfulate must bc correct.
il,#.,'l',fi
Justillcatlon ofthe abovc postulates :
,6 lstdbutlon o,
e
collisions, though some molecules are speeded up, i
some otlers are slowed down and hence the frac-
tions of molecules possessing particular speed
remains constaEt at constant temperature. This is
,=\E=tr=
called Maxwetl-Boltzmaaa dist bution and is
rvhere d : M./V is density of the gas
shown by the curves in Fig. 2.15(a) for two differenr
t€mperatures. Tlpes of speeds, It moy be tntcd that thcre are
lhree types of speeik ol gaseous molccules whirh are
z commonly used- These are
z
(i) Most probable sPeed (a). This is lhe sPeed
u,
fzrlt possessed by lha maximum traction of
)f
uJ
MOST
molecules.
o PBOBABLE
ul SPEEDS
o (ii) Root Mean Square (RMS) spe€d (u). 1, ts
the square root oI the mean ol tlu squares of the
o speeds ofthe molecuks. Thus iI u,uz,u3....u ndre
z lhe speeds oJ n molaules then
o
O Root Mean Square sPeed (u)
(!
IL
MOLECULAR SPEEDS ul+o!+ ... + v2,
R
EE
FIGUBE 2.15(a). Maxwell's distribution of (ii) I, is tlu wemge oI the
speeds at two diflerent temp€ratures
Average speed (u).
AR
ut+uz+...,+un
sryl (u) =
S
POSS h'emge
N
and
IA
:il.'
a= r/y _i,l
IRT
Explanation on the Basis of Kin€tic Theorf,. nut j rrau'? = Kinetic energy of the gas
According to Kinetic theory of gases, at constant
temperature, the average kinetic energy and hence R
.. )
; K.E.
EE
the average speed of the molecules is constant. PV = ...('
AR
reduced to one half of its origina.l volume. The same K.E. c( Absolute 'Ibmperature (T)
N
IA
number of molecules with their same average speed or K.E. = /<T ...(r,
IIT
will now have half the original space to move about. where & is a cosstant of proportionality.
As a result, the number of molecules striking the
unit area ofthe walls ofthe container in a given time Putting this value in equation (i), we get
.,
will get doubled and consequently the pressure is Pv =
also doubled. Conversely, if the volume of a given ;kr
mass of a gas is doubled at constart temp€rature ,2
As is a constant quantity, k is also a con-
(Fig.2.16) the same uumber ofmolecules with their i
same average speed will nowhave double the space stant, therefore, if T is kept constant, kT wilt be
3
constant. Hence PV: constant, ifT is kept
GAS constant, which is Boyle's law.
MOLECULES
IN MOTION
(2) Charles' Lav
ExplanatloD on the Basis of Kinetic
-.1
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2128 Pradeep's
move faster (Fig. 2.17). As a result, the molecules numbcr of times per seccnd as ifno other molecules
ofthe gas *ill strike the unit area ofthe walls ofthe
container more frequently and vigolously. Conse-
quently, the pressure of the gas will increase ac-
cordingly. Thus, at constant volume, the Pressure
of a gas increases with rise in tcmperature. This
explains the Pressure Law.
vr'hen prcsent alone in that space. Hence the
Kinetic theorl,explains Dalton's Law of Partial
Pressures.
Deductlon from Kinetic Gas Equation. Let us
consider only two gas,?s. According to kinetic gas
\/ .
equation,
7 mnu2
w = \mnu2 or rP =:3 v
\"/, Now, if only the ffust gas is enclosed in the
vessel of volume V, the pressure exerted would be
be
in the same vessel then since the gases do not react
by
with each other, their molecules behave inde-
C
ga
N
exerted would be
explains Charles' Law.
IA
R
EE
AR
mo
I? rrRT
S
2 n,u,
Solution. Average spced (u.,) (Molar mass of CH4 = 16 g mol-l)
2n,
= 7482.6 I
10x4+20x5+,10x8 lQ 56.r-t
l0+20+q = =6 Average K.8.,
JK-l mol-l
Root mean square speed (ur.m.r.) ree.=|m =)" 6.02 8'314
x 10r molecules mol-l
a|ffi.ffi
' 2n, ' 10+4+40 = 6.21 x 10-2r J molecule-r
X3OOK
o, = ]nt *ot-r
160+500+2560
= 6 78 ms-I = I x 8.31a JK-l mol-r x 300 K
Most probable speed (u-) = 3741 3Jmol-r
= 0.916 x u,...,
= 0.816 x 6.78ms-l = 5.53 ms-r.
(D)u,,.,,.=tr
r i.\.1\lt,t.i.t I @) Colculate the totql qnd Using C.G.S. units, ptrt
average kinetic energ oI 32 g methane moleculcs at R = 8.314 x 107crgsK-lmol-l,
27'C (R : 8 3141K-1 mot-1) T:27+273=3C0K,
(Bihar C.E.E. 1997, N.C.E.R.T,) M (for CHo) = 16g mol-I, we get
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430
l'radcay's Netq Course Chemi stryaifrlll
l-,
.,:v "t'16 *:r+, to' , eoo
=6'E39 x ld cm s-l
(i) For an ideal gas, as PV : nRl, Z : I
= 6t3 9 ms-l
1 (fi) For a real gas, as PV + nRL Z*1. Hence
using S.I. units, put R = 8'314 JK- mol-l,
two cases ari6e :
:
T 300 K M = 16 x 10-3 kg mol-l, we get (a) WhetZ < l, (e.g for CHo, CO2 etc.) the
3x8.314x300 gas k said lo show negative deviarion. This implies
16 x 10-3 that the gas is more compressible than expected
from ideal behaviour.
= 6E3'9 ms-r
This is also attributed to predominanc€ of at-
tractive forces among the molecules of these gases.
r.6
No. of molecules in 1 mole of the gas
o
C
1.4
F
(Avogadro's No.) = o
f
S
f; 1.2
N
B ou
H 06
tL
^> 0.4
o
Ideal and Real Gases.,4 gaswhich obeys lhe
ideal gas eqtation, PV : nRT under all conditions of
lemperature and pressure is called m \deal gas'' Hr:w'
cver, there is no gas which obeys the ideal gas equation
9,.4 K
(I 273 K
under all conditions of temperature and pressure. o .".023 K
Hence the conc€pt of ideal gas is only theoretical or 5 r.z
hypothetical. The gases are found to obey the gas laws f-
fairly well if the pressure is low or the temperature is
high. Such gases are therefore krown a s 'Real gases.'
O=''o
d)
IDEAL GAS
pressures, CO2 shows much larger negative devia- low, the gas molecules come close together. Hence
tion than H, or Nr. under these conditions :
For the same gas, at a particular pressure, the (!) The forces of attraction or repulsion be-
tween the molecules may not be negligible.
extent of deviation depends upon temperature, as
shown irr Fig. 2.18 (b) for the case of N, gas. (ii) The volume occupied by the gas maybe so
small that the volume occupied by the molecules
Plots in Fig. (b) show that as the temperature may not be negligible.
increases, the minimum in the curve shifts upwards.
Equation ofState for thc Real gases (yan d€r
Ultimately, a temperature is reached at which the
Waal's equation), To explain the behaviour of real
value of Z remains close to 1 over aa appreciable
gases, J.D. van der Waal, in 1873, modified the ideal
range ofpressure, For example, in case ofN2, at 323
gas equation by applying appropriate corrections
K, the value ofZ remains close to 1 uplo nearly 100 so as to take into accouDt
atmospheres..
(r) the volume of the gas molecules, and
Ilp tempcraan O whlch a r*l p bduva Eb an (r'i) the forces of attractiotr between the gas
idal gas owr ol aryrvioble prrvrr ranrye b molecules.
atld @etfst[Exlltur€ar Boylc polnt. He put forward the modified equation, known
Further from the plots shown in Fig. 2.18, it after him as yan der Waal's equatiou.This equation
may be seen that at ordinary pressures (1-10 atm), for 1 mole ol the gas is
Z rs very iear to 1 i.e. the deviatious from ideal
behaviour are so small that the ideal gas laws can
be applied.
(r.#)ry-D)= Rr
Causes of Deviation from Ideal Behaviour. As R
EE
andfor n moles of the gas, it is
explained above, the real gases obeyidealgas equa-
AR
marked deviations from ideal behaviour. The where'a'and'b' are constants, called van der
N
The derivation of the gas laws (and hence of DerivatioD ofr,on der Waal,s equatio[. Van der
the ideal gas equation) is based upon the Kinetic r*hal's equation has been obtaincd by modifylng the
Theory of Gases which in turn is based upon certain ideal gas equation PV = ,I{T by applytng corrections
assumptions. Thus there must be something wrong for the volume and pressure.
with certain assumptions. A careful study shows (i) Corrcctior for volume, Suppose the volume
that at high pressure or lou/ temperature, the fol- occuprcd rythe gas molecules is r. When themolecules
lowing two assumptions of Kinetic Theory ofGases are moviDg, their effective volume is four times the
actuaf volume ie. 4 u. Let us call it, ie. b = 4t(Callen
are faulty :
excluded yolume or co-volume). Thus the fteevolume
(i) The volume occupied. by the gas molecutes availablc to thc gas molcculqs for movement ie
is negligible as compared to the total volume of the Correcled volume = (V
qqs.
- D) for one molc
or = (V - nr) for n moles
(ii)The forces of attraction or repulsion be-
Qi) Correction for prcssurc. A moleculc (A)
tween the gas moleales are negligible. lyiog within the vessel is atiracred equalty by other
The abovo two assu-Eptiors are trueonlyifthe molecules on all sides bur a molecule near the wall (B)
preisure is low or the te.Eperature is high so that is aftracted (pulled back) by the molecules inside (Fig.
2.19). HencE it qens less pressure. In other vords,
the distauce between the molecules is large. How-
observed pr€ssure is less tban the idealpressure. Henc€
ever, if the pressure is high or the temperature is
Crrrected prcssure = P +p
+It iiraybc > 1\r1e: T >
Pointed out that ior H2 and He. Z, 2?3 K and rncrcascs with inctcase in prEssure Al temp€raturc
much below 273 K, Z < 1 elrn for these gases-
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2132 Neut Course Chem istr1lm)
Unlts ofvcn der Waal's constatrts
WALL OF THE (i) Unlts of 'E'. As
VESSEL
an2
' v2'
... A=.
Dxv
1
n-
= atm L2 mol-' or bar dm6 mol-2
(ii) Units ofrb'. As volume correction
u = nb,
MOLECULE 'A' MOLECULE'B'
.'. b=9n = Lmol-l ordmtmol-l
FIGURE 2.19. Baclarard pull oIr moleculc
B by other molecules. Explanailon of the behaviour of Real gases by
van der Waal's equatlon
Evidcntly, the conection term p is proportional (r) At very lorr prtssurcs, V is very large.
to dcDsity ofthc gas ncar thewalland thc dcnsityofthe
Hehce the correction tcrm a/\P is so sDdl that it
gas insidc ie.
can be neglected. Similarly the correction term 'b'
p
" (densityf orp - d2
can also be neglected in cornparison to V. Thus van
[]ut d. Vforonemolc I
der Waal's equation reduces to the form PV :
RT.
This e:rplains why at very low pressures, the real
or d' Sfornmoles gases behave like ideal gases.
(ii) AtR moderate pr€ssures, V decreases.
llence 2 d I for onc mole or p = a 161sns rn91s a/V
EE
Hence increases and cannot be neglected.
v2'v2 However V is still large enough in comparison to
AR
'v
IA
ot
IIT
co-volume.
RT=1*RT
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STATES OF MATTER 2/33
PROtsLEMS ON
l.\ \\l!,1_lj I Calculste the prcssurc excrled by
110 gof carbon dioide in a vessel of 2 L capscity at m
37"C. Given that the van der Waal's constants are at 10 bar pressure. Given that Ior SO2 gas, van der
a : 3. 59 L2 alm ntol-2 arul b = 0. 0427 L mol- t. Waol's constants ate : a :
Comparc thevaluewiththe cqlculatedvalue if the gas R 6.7bar L2 mol-2 and,
EE
b = 0.0564 L mol-l.
were considered as ideol.
AR
tron
S
b.4\ N -nb)=n.r
\ v,/' (r.#)(v-nr)=aRr
N
IA
nRT
ot ^P=v-nb-nzsn2 _ (p + anztvz11v -
IIT
nb1
nR
As pressurc is in bar, takins R = 0.08J L bar
n = 1.'9 =
Here,'44 ,'t molus. Substituring rhe
K-l mol- I and substituting thc frven values, wc gr-t
given values, we get
[10 bar + (6.7 bar L2 mot'z) (z mol)z / (5 L)2]
(0.0821 L atm K-l mol-1) (310 K
P= 2.5 mol) T= 5L-2molx0.0564Lmol-1
(2L - 2-5 mol x 0.0427 L mol-l) 2 mol x 0.083 L bar K- I mol- I
= 0'7ll or ,:1"*xL.32x10-73
For ideal gas, Z: lor thc given gas
1. As
Z < l, it shows negative deviation i.e. it is more
=315x10-24
compressible than elpected from ideal behaviour.
.ll\\\ll't,l! The van der Waal's constant'b'
.. 3logr = tog (3 15 x 10-z)
for orygen k 0 03
' 18 L mol- 1 . Calculate the diameter =-24+0'4983
o! the oqryen molecule.
= - 23'5017
Solutlon. b = 4u
or logr= - 7'8339 =S 166l
0 0318-
-
^, ,, =!-44 7.95 x Io-3 L mot I
.'. r = Altilog 8 1661
7.95
=2xr=2932x10-8cm
6.02 x 104 R:2'%2 L
EE
AR
C
a 0 dm3 vesscl at 25"c (a) using ideal 88s equa- temperature of the steam. Given that for water
IA
.
3
tion (6) using van der Uaal's equation The van der
a = 5.46bar l] mol-z
IIT
vapour. and
vhal's constants arc i o = 4 17 daf atm mol-2, KI
b =0 031 Lmol-l. Ituls. 1531 7
6 = 0.0371 dm3 mol-1
[{lrs (a)4 9atE(r)4 Eatml
Dillerence between ldeal gas aorl Real gas. The main points ofdifference are summed up in the table
below :
(i) It obq/s gas lau/s under all conditions of tempera- (i) It obels gas Iaws only under low pressure and high
ture and Pressure. temperature.
(ii) No gas is ideal. (ii) All gases are rcal.
(ri) Volume occupied by tbe molecules is negligible as (iii) Volume ocrupied by the molecules is not negliSible
compared to the toull volume occupied by the 8as. as compared to the totalvolume oc{uPied by the 8as.
(iv) The forces ofattraction among the molecules ofthe (iv) The forces ofattraction among the molecules cannot
gas are negligible. be ncglected at high Pressure and low temperature
(v) lt obeys van der rihal's cquation
(v) It obeys the idcal 8as equatior PV = nRT
(rr#)ry-rb)=nRr
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STATES OF MATTER 213s
tTessure 61 14. I 26.r 44.4 )6 .5 7t.2 73.9 in 1861 was the first to study the critical phenomena
(atm)
C
Further, observcd that gases like of pressure on the volume of CO, at different con-
N
hydrogen, helium, orygen nitrogen etc. could not be stant temperatures. Some of the isotherms thus
IA
as that
uJ
above vhich it cantnt be t
liquefuil lwwsuver higft pressure may be applied l
o
U)
on ehe gas. IJJ
E,
(L
VOLUME, V
-+
represented by T", P" and V". For example, critical FIGURE 2.20. Isotherns of CO2
(From Andrew's experiment)
constants of CO, are :
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2136
Neut Course
At the lowest temperature employed i.e. thus be cooled is called thc invenion temperatwe.
13 1"C, at low pressure CO2 exists as a gas, as The inversion temperatures for hydrogen and
helium are -80'C and - 24O'C respectively.
shown at the point A. As the pressure is increased,
thc volume ofthegas decrcases alongthe curve AB. The process based uPon the above PinciPle is
At B liqucfactiou of the gas starts. Hence volume known as Lit de's process. The apparatus used is in
dccrcasis rapidly along BC because liquid has shown in Fig. 2.21-. The chart showing the names of
much less volume than the gas. At the point C, the different parts is also given in the Fig. 2.21.
Iiquelaction is complete. Now the increase in pres-
sure has very little effect upon volume because
liquids are very little compressible. Hence a steep
-.>
ctrrvc CD is obtaincd. As thc temPerature is in-
creased, horizontal portion becomes smaller and
smaller and at 31 1'C, it is reduced at a point, P.
This means that above 31 1"C, the gas cauot be
liqucfied at maY be aP-
plied. Thus rature. The t
correspond gas at the t
criticai tem ure, P" (i.e.
t
73 9 atm). The volume occupied by 1 moie of the
gas under these conditions is its critical volume,
v. (i.e. 95'6 ml).
2.12. Methods tor Liquelaclion ol Gases ,,r:iii:i; ,, R
EE
TWo methods most commonly used for li- air c
AR
A = lnlet fo.
quefaction of gases are briefly described below : B = Compressor E = Copper sPiralwith a jet J
c F = Ouler chamber
= Condensing coils
C
pand adiubaticull! through atine orilice (hnle) into The above apparatus was used by Linde for
a region o! ltw pressure, it is accompanfud b! the liquefaction of air. The procedurc adoptedis as
cooling.
follows :
The term 'adiabatically' implies that the ap- Thc air is first compressed to about 200 at-
paratus is perfectly insulated so that no heat is lost mosphere in then Passed
to or gained frorn the surroundings. through the c csult, the air
An obvious reason for [he cooling is that when is cooled and condense to
the gas cxpands frorn a region of high pressure to form the liquidwhichis removed. The dry air is then
the iegion of low pressure, the intermolecular dis- passed through the copper spiral E which ter-
tanccs increases. Some work is done in seParating minates iEto ajet J. The air expands through thejct
the molecules apart. This is done at the cost of J into the chamber F where the pressure of the air
kinetic energy ofthe gas. Thus the kinetic energy of falls down to about 50 atmospheres. Thus as aresult
the gas decrcases and therefore the temPerature of JoulcrThomson effect, the air is cooled. As the
falls. cooled air moves uP, it further cools the incoming
air. The cooled air is sent to the compressor again
and the process is repeatcd a number of times till
ultimately the air is cooled to such an extent that it
(empcra- liquelies. The liquelied air collects at the bottom of
sascs arc first cooled to some particular ihc chamber F and can be drawn off. Any uncon-
iure and then allowcd to expand, thcy behave like
densed air is recirculatcd.
other gases. Thc tcmperaturc to which a gas should
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STATES OF I\,4ATTER
2/37
--)
2.1 3. lnportance ol Critical Temperature
::+::j:,:r:ri.::ii;,:,i:r:
R
EE
t:-:::-:::_:::::t
AR
C
S
N
IA
He H2 Nz co .q- NH,
\ (19 s.2 33.2 D62i4.o N4r-4os o
d @nLz O 0347 o.Ul t.Sg--t ag 3.5g 4.17
1. ShaPe.Liqu
take up theshaPe of
This is because the
state of co$tant raPid motion'
rne.This
action in
the gas
mpletelY
R
EE
free to move.
AR
C
S
N
IA
pres
I
IIT
mol
rcmPeruture.
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STATES OF MATTER
then initially, as there are no molecules of the (a) Naturr ofthe liquid. Ifthe intermolecular
Iorces o[ attraction in the liquid are weak, the
molecules can casily leave the liquid aIld come into
lhe.vapour phase and henc€ the vapour pressure is
highcr. For example, the vapour pressure of
R
EE
acetone, benzene etc. is higher than thrt ofwater at
the same temperature (as shown in Fig. 2.25).
AR
LIJ
(!
IA
l
a
IIT
a
tu
d
(!
(!
l
o
I I
I I
.---+TEMPERATURE
attmspheric Prexure).
and so does the vaPour Pressure'
a
uJ
J fz, It
f
o
UJ
J
o
=
TL
o
z
o
F
o
ttL
R
EE
AR
tu
increased till the vapour pressure De.cornes equar
IA
respects :
,ti".pfr"ti" pr".rri",
qtmosnheric Dressure. the vapour in the form of
IIT
EVAPORATION
forces
Obviously, greater the intermolecular
is the heat
of attraction pi"I""t in a liquid, greater
FIGUBE 2-27.Bolingof a liquid'
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STATES OF MATTER
2141
of point. For from position CD to position EE Thus some work
ex iling point has to be done against the force of surface tension.
of acetone'
be '
7. Surface tension. Surface tension is a char-
acteristic property of liquids which arises due to the
fact that the moleculcs of thc liquid at thc surfacc
are in different situation than those in the interior
face tension.
IA
S
IIT
5ome importanl.
results o[ surface tension
are bri
FIGURE 2.28. Surface tension oI a liquid.
.i
CAPILI.ARY
teimolecular forces and, therefore, are said to be
IA
TUBE
more viscous or are said to have high viscosity' On
IIT
u cm/sec
-FIGURE 2-32. (a) Water rises in the-capillary
-
- iUt l,,t"t.ury 'level
falls in the capillatv' u+du cm/sec
Allparts of the
tube with the same
be made uP of a large
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STATES OF MATTER
2143
coaxial layers. The layer which is in contact with the Some Important Results. Some important
walls of the tube is almost stationary.
*ith the property of viscosity are as
results related
As we move from the walls towards the centre follonn :
of the tube, the velocity of the dindrical layers
keeps on increasing till it is maximum at the centre. (i) Uoits ofviscosity. As already described,
Conversely, we may say that as we move from the d1)
c lls, the velocity of the layers 4Ad*
k In other words, every layer
o or friction to thelayerimme_ f.tu _
d A. d1)
-_mXsXdx gXcms-2Xcm
cm'X-i -sT
,l__..._._
T
A 'Aa
R =gcm ,s ,
EE
*
* = lgcrn-1s-l
AR
i.e. 1 poise
u=0
C
its
:,lri l. Surfactalts. Soaps aod delergents which when added to water d€creas€
'surfxctants' (surfacc activc cqcl'ls)
liouton'sRule.Forliquidswhicharenoo-assoc'Jledarldwhichdonothavetoohighboiliogpoints'theratio
of rhe heat ofvaporisation (o lhe boiling point is approximately
88JK-l ie
?-tt.I*-'
Guldberg's Rule. The boiling point of a liquid is nearly
two{hird of its critical temperaturc when both are
The reciprocalof the coefficieDt ofvlscosity of a liquid is called its fluidity e O=;
'
the effect of temperature on
Effcct of teEperature on surface tension (Eotvos equation)' Quantitatively'
surface tension (z) is given by Eotvos equation, viz
,=uu,_Dlk)r,,
temperature of the liquid '/< is a constant aDd I $
where p is density, M is molecular mass and;c is the critical
the temperature at which measurement is made'
: temp€rature' surfac€ tension of the hquid is zero Ai
R
Thus, when I = lc, / 0 This means that at the crltical
EE
vapour disappears'
this point, the meniscus b€tween the liquid and the
AR
-
called aoi'/adon energl for viscous flotn''
S
SDC"TION_III
TIIE SOLTD STAIE The various solids are classified into the fol-
lowins two tvpes :
[fl Crvsiaffine solirts. All solid elements and
compounds
Am (2) glass, Pitch,
fused silica, r mass etc'
Points CrYstallin€
solid and an AmorPhous solid.
(,) Risidity
(ii) A defrnite shape and a definite volume
(rii) IncomPressibilitY
(iv) Poor diffusability through them
(v) No fluiditY
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STATES OF MATTEB
2145
FIG ergoes
o o a
C
,.o.O
S
N
IA
FIGUBE 2.35. Anisortopy o(hibired by Thus thc main points of diffcrence bctwecn a
IIT
(r) The coDstituenr parricles are arraDged in a rcgular (, Thc constituent particlcs are not arraDged iD aDy
fashion containing short range aswellas long ringe regular fashion ; there may be at the mostsomeshort
order. range ordcr only.
() They have sharp metriDg poinrs. (!r) They mslt ovcr a range of temperature.
(iii) They are anisotropic. (iii) They arc isotropic.
(iv) They uDdergo a clcan cleavagc. (-) They uDdergo an irregular cut.
Molecular Small molecules van der Waal's for- Soft, lo$,r m.p., volatile, Solid CO2 (dry ict),
ces electrical insulators, Poor CHa, wax, iodine, ice,
thermal conductors, lor (Ss),
sulphur Phos-
heats of fusion
phorus (P1).
C-ovalent Aloms chemicaltY Covalent bond for- Very hard, tligh m.P., Poor Diamond, silicon
bound bgether in ces co[ductors of heat and carbide, silica, quartz.
the form of a net- electricity, high heats of
work fusion
4. Metallic Positive ions and Electrical attrac- All metals and some al-
mobile electrons tions (melallic loys-
bond)
R
EE
AR
C
S
N
Ionic solids do not conduct electricity in the solid state as ions are Dot free to move'
IA
iti:, l.
IIT
Na+ lon
ion
.lAcovalentsolidiSagiaDtmoleculehavingathrcedimeDsionalneiworkofcovalcntbondse'&struciureof
diamond is shoPn iD Fi8. 2.38 on the nexl page'
]Thevalenceclectronsofametalatomarcfreeelectrons(asiorceofaractiononthcmbythenucleusis
minimum;. Leuuing valence elecirons, the remaining portion isa Positve i n,called "kernel"'
The free mobile
electrons hold the kernels together.
The simultaneous airaction betweenthe ktmeb aml the mobile clectrons
,rhich hold the kernels logether c called
metallic bond.
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STATES OF MATTER
2147
(FREE/
Thus metgllic bond spreads over the whole crystal aod is Don- directional. Tbis model is called,,electron
sea
model" (Fig.2.39)
. 'Ihc order of melting poinrs ofdifferent rypes
of cr)dalline solids is as fouolrr:
Co!r'aleot > Ionrc > Metalic > Molecular
(_ 4000 K) (_ l0o0 K) (ss0-1000 K) (273-600 K)
''lf]emeltingPointofasubstanc€rs-ameasureofthemagnitudeofthebindiDgforceamonglheconstitucnt
particles. For example, tbe order of melting points and hance that of lhc binding force for i few rrurt"n"",
are given b€lo\r, : R
EE
oz <Nz < qHsoH < H2O < C6H6 < Na < NaCl
AR
ual ,ue?tion?
(? | Airange solid, liquid and gas in
order of c,lerBi giving rcasoDs
Ans solid < Uquld < Gas. This is because a solid absorbs enerry ro chaoge iDro a liquid which furrher absorbs
enerry to change into a gas.
(l l ' A eas is lilled into a bulb connected to an op€D
limb marometer. The diIlercnce irl the levels ofthe two limbs
is 2 1 cm. The atmospheric prcssure is 740 mm. What is the pressure
of the gas ?
Ans. 740 2l = 719 mm.
lJ t How-do you convert
(a) pressure in atmospheres into SI uDits ?
(6) tcmperature in oC to temperature in .F ?
Ans.
1a; 1 atm = 101, 325 pa or Nm -2 or I bar = ld pa
(r).c=;cF-32)
{J I What tyae of graph r+ill you get rvhen ryis plotted lgainst p
at co[statrt temperature.
Ans. A srraight line parallel ro pressure ards.
Q -i Hoy is the pressure ofa gss related to its density at s particular
temperstur€ ?
,MP
Ans. 4 =
RT
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Ncu,r Course Chem istrtl
a 8as iD a hixture relat'd to the total pressure of thc Etrseous mi'cur€ ?
Q. 6. How is the partial pressure of
'Ibtal Pressure'
An$ Partial prcssure ofa gas = Mole fraclion of that gas x
speed ond root Inean square sp€ed on
Represent the rclative values of most probable sPe€d, avcrage
M;xweu's distribution curve for sPecd$
Ans. Refer to fig. 2.15 (b) Page 2D6.
ofa gas
1. r lvhat is the relationship bet*een svcrsge kinetic ener-A/ and the temPerature
?
Molecutar ma;s of
N
IA
=,oon
H",ffi=ff=l/$
IIT
P,! .
tr=u, ttul,L.
o. ,. = lt Vz
""
,rn*. -f
T,
. P. Tz r"o , zor l-!,] z:
llfrrd. +.uencc Pz- -Tr [dz) - -- i- tr0r ='J
= z--.
""""'
lTrl-
r.i i l. lvhflt\ ould be the SI unit ror thl qrlantitypv2T2 'a ? <N'C'E'R'T')
tu" t*._1qL]-6f.
= Nm4 Kz mol-r
_273.C is the lowest temPemture. (,|[c.E.R.r)
, ) !iIn terms ot charles' law explain why
Ans. At volumc of the gas becomes equal to -cro i c the gas ceases to exist'
-273"C, stronger
(-) tr, Critical temperature for CO2 and CIla are 31 l'Card-tl 9PC respectiYely' Which of these has
(N'C'E'R'T).
intcrmolecular forces and lYhy ?
bc liqucficd-iJ glcatcr arc thc intcrmolecular forcas
-"'
'Ans, Highcr
lhc crilical temPcrature n)orc easlly lhc tcs c.1n
cb, has stronger intermolecr lar forc€s than cHl'
oiiiiir",ion rrence
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STATES OF I\,4ATTEB
2149
Q. I7. What is the ratio of average kinetic ener5/ oforygen rnolecules to that ofozotre molecules.t 27oC ?
Ans" Av€rage kinetic erlerry of any 8as depends olly on temperarure aDd
not upon the nature of rhe gas. Hence
botb the tases will have same average kine tic erlerg aL ;.1.C i.e. the r rtio wlll
be 1 : I.
Q' lE what is thc dillcrene hctneeo toa.I tiretic eaergr and tratrslatioual kiletic energr ? For r,hat t!,pc of
]tlole(ul€q the two orc equsl ?
Ars. al kineuc eDertics. The total kinetic
(He, Ne etc.) as they do not possqss
Q. l9.Out of N, End NH3, rrhlch orc rvill have grraaer volue of.a' ardrhich ore rvill hove greater r.alue of.b, ?
ADs' (0 As NH3 is more easily liquefiable (due to hydrogen bonding), itrtermotecular
forces of attracdon are
stronger than in N2. Hence NH3 will have greater\ralue for ,4,.
(ir) As NH3 molecule is larger in size thaD N2, henc€ NH3 will have greter
value for ,r,.
(For NH3, a = 4.lz L2 atln mol-z, D = 0.0371 L mot-r
For Nr, a - 1.39 L2 arm mot-2, b = 0.0319 L mol-l)
Q loyyhot f,ould hrve happered to the gas if the Eolecuhr colisiotrs r.re [ot erastic ?
Ar& On ev€ry collision, there would hav€ been lo0s of enerry. As a result, the molecules would
have slowed Jown
and ultimately settle down in the vessel.
Q. 2 cor ls hcsvrcrthsr 02 rId N' goaes pEsertrn the air but itdoes Dotforo the rowerraycrofthc etmGphere.
Vihy ?
ADs' Gsses possess theproPeny ofdiffiJsion.which is indepeDdeni ofthe
R
force ofgmvitarion. Due ro diffusion, rhe
EE
gases mix into cach other and remain almost uDiformly
distributed in the atlisphere.
Q 2'{ro ond co2 have ahc saEG rrt€ ofdifiusioD u,der ss,e coBditio,s ort€Eperature ond prcssur€. why ?
AR
Ch a m i sl tqi:@
(-). r I . Why liquids diffuse slowly as compared to gases?
Ans. In liquids, the molecules are less free than in a gas r.e. the intermolecular forces (van der waal's forces) in a
CARRYING 1 MARK
Q.l.Whichstateofmatterhasadefinitevolumebutnodefiniteshape?
Ans Liquid.
Q. 2 . What is the equation of state of an ideal gas for z moles ?
Ans. PV = nRT
(). -1. What is the value of the gas constant in S'I' units?
Ans. 8'314JK-l mol-l'
Q J. What is compressibility factor ?
R
EE
Ans. ,_PY
"-nRT
AR
(t * (v--J) = RT
S
fuis Poise.
Q. e. vtrhat is sI unit of coeflicient of viscosity ? How is it related to poise ?
Ans SIunit=kgm's
-1 -1 ^
Poise=1gcm'.s'
-r -1
16. Write kinetic gas equation. How does Charles, law fouow from it ?
,, .!1r.1, or*"
C
1t'
N
what is 'compressibility factor' ? what is its value for 'an ideal gas'
? How does it herp to understand
IA
19. Why do rcal gases show deviation Irom ideal behaviour ? Wtite
van der Whal,s equation for ,, moles
ofa gas.
20. What are the unib of van der Waal,s constants ,4, and 6, ? What is rheir significance
?
Scc 2.1I 21' Why is rhe effect of temprature more important for trre ritueraction gases of ? Define critical
temperature and critical pressurg.
22. Detine Joute-Thomson effed- Why hydrogen and helium show
exceptioDal behaviour ?
23' Brietly descrjbe the rmportancr of criticar temperature. How
can it be correrared withvan dcr wbals
constant a' I
Sec.2.l,l. 24' Exprarn thc statemenl 'Llouid srate is intermediate between .he gaseous ,
state and thc solid statc
Io 2.15. 25.
26. Give reasons for lhe following:_
(i) Liquids have a definite volume bur no definite shape.
(ii) Liquids have higber density rhan gases.
(iii) Liquids are much less compressible ttlan gases.
(rv) Liquids possess fluidity.
27. DefiDe vapour pressure, boiliDg
[rcint and heat ofvaporisanon.
2t. What is differeDce beNeen BoiliDg aDd Evaporarion ?
29. Explain rhe effect of temperature on the follo ing:
(i) Surface rcnsion (,f) Viscosity
tiii) Vapour pressure (iv) Dcnsity
30. cive reasons for the following:
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Pradeep's
and a 8as'
Sec.2,l. 1. List the main points of differencr between a solid, a liquid
explain why substances exist in ihre€
Sec.2.2. i: il;; ffi;i iltermolecular forces ancl thermal energr,
different states.
Sec. 2.3" 3, How are the following measured ?
(i) atmospheric pressure (ri) pressure ofa 8as'
of this law
Scc.2.4. + 5ir" Boylct lii. How is the lai verifred graphicaly ? what is the sigoincanc€
b the""o'*pr"lit
mountaineers?
zcro' ? How is this law
5. State aDd exPlain Charles'law. Hotr'does it lead !o tbe coocePt of'absolute
made use ofln the meteorological observations ?
or Brieflv exDlain the Dynamic Panicle Model or the Microsc'Pic model of a 8as'
IIT
R
EE
AR
C
S
N
IA
IIT
t-
rl
I
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Thus TB > Tc
C
S
N
IA
IIT
r,=?1
nthemole$lesofaSascomeclos€toeachother,astage@meswhenthe
when thev are clGest to e,ch
reDu di:il;;;;;-J;ntres of rhe molecules
diameter (o)'
tars uetween ttrem is called molecular
Li#
molecules
2lg
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STATES OF MATTER
215s
ADDITIONAL UgEFUL INFORMATION
Free paths.
$=ift
.
C
becomes I= .-1_'
./r;aNRT
IIT
FIGURE 2.42. plor of log p rs log V. FICI.JRE 2.a3. iot of log V vs log T
Acrording ro Charles'taw,
{ =
"onr,.
Iog.V-log T = cqns1. s1 v = tog I. + consr.
-- plor of log V vs log
Hence
log
T will be as shown in Fig. 2.43.
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Pradeep's
riquid
is fou
il'"*";:'ff:"'Hi#:u1iJ:liH":
the
"*tull. *.u"u"".c.t called strlcmomcte. It is based uPon
of surface tension' The aPparatus us€d. is falling from
orinciDle ihat rhe surrac" t.nsron oru iiiiii'ir
li,:"iii,ii"p".ional the mass Jf the spherical drop
to
(\ / h = mr / m2)
t4
I *piiru.y trbc
princiPle
rr"ro
'ertically
3"##il#J:ff:'H:ffilJ5i"x[
eir times of flow.
R ofa liquidwith temperature The
EE
" '1i"r.*ro"'"hPeyron equotiotr' It gives the variation ofvaPour Pressure
AR
equatioD is
P,, ^IL rT2
- Tr)
C
r.8p; = t.msE
I-TE-J
S
N
IA
o
iDg poina.
(ii) Ditrmond has a yery high Eelting poinL
(iii) Copper is mallesble and ducdle but brass
is hard and briatle-
I R
lz,
EE
AR
C
Point.
=R'146=l+6R
Hence increasint order of dcnsity will be 02
at
=- FTGURE 2.45.
C
l**4)
v'l rv-al
' =nr
\
- -RTa
v=y-:g- yZ
= 2a.97 E,rn.
C
ar l600IC
Sotqdgu. l0Lat 200 atm
IIT
creas
lume gxPansMty of a 8as means ln-
in volune per degree rise or fall in or 35
zg=
,1-+.
temPerature of its volumL rt0"C
,,. '2
V,=Vo+0 0037 xVox' or Mo.=?lx
lfi,) =4t 7't'
=vo(1 +0 00370 ch will dilfuse faster' ammonia or
Coz? relative rntes ofdilTusion ?
At 100'c,
x (BITRL'tchi1989)
V166'6=V6(1 +0 0037 100)
Mcoz = 44'
= 685 cm3 (Gi!en) NH3 = 17',
or vo = ,615, =
soo
"'3 .r. , . ' { fr , hence NH3 will dilfuse faster
At
-100'C, x (-
V-100'c = 500 [1 +
= 315 cm3
O 0O3? 100)l
'n*,-!E = \[4 =,.oon
Eo]-' MnH, ' tt
I'rorl. ,, 9 Calculate the temPeroture at which at 27oC is heste'l utrtil
Zt g oi N, t"itt o"""Py a volume of lo o litres et
2 46 nrrrt t"* I S -l,' op,en
"ess'l
atmosphere. (M L'N'R' All*luhad 19E7)
28 g N, = 1 mole of N2-
APPly'og PV=nRf R
2'46 x 1O = 1x0 0821 x T- This gives
EE
'l = 299 6K the vessel is oPen, Pressure and
volu ifnl moles are present ar
AR
staot. Thus
t,l)tot' 10. AtlE"C and 765 torr' I 299 L ofa
gas
moles are Present at T2, we can write
t,t 'l't
*.lnrr" liii e. moleculEr and ,12
C
PV=n,RT1 ; PV =nrRT,
N
Solutior. Temp. ofthe gaswhen both the flasksare Thus in the same time (10 mioutcs),0.4 mol of
imme ling water = 100'C = 373 K. N2 and 0 . 1 mol of unkDos|n gas diffuse out.
C
mersed in ice and the other io boiling water ber of moles, applying Grahao's law of diffusion
*q**= G-
IIT
o +r1oo
= = 5s.6 = 323 K
-p.p2
As volumtemains consEnt, +.I _E ," 3-f=E * Mx=44E8mol-r
o 5 P2 problern I E.Calclllala the ioot EGan squarE slreed
311 - 321 (azs) of ozone kcpt iD a clo6€d vesi!.| at 20.C aDd
1r1 pressure olEZ cm of IIg. (Bihot C.E.E. 2003)
or Pz=ffir 0 5=0 433 etm. Volume oc{upied by I mole of 03 at
I,r,,r'rrnr lr'.What is the dilference ih pressure 20oc and 82 cm pressure can be calculated as follows :
/
,=v#
='76 cfii x o.gg E crn3 x 981 cm / s2
.3E x
1| 3 x82x 13.6x981 x 22282
- I ---
= ? 104 dynes cm-2 4a-
= 0.073atE (I atm = I.0t3 x t06 dynes cm-2; = i 90 x toa c[Vsec.
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2162
-1'7
n a 0 751 L2 alm mol-2 or P =ix;x 1.365 x lO-acm3
'"- nE-i;A.or%L^rrry
=54 5rtm = 3 251 x 10-24 cm3
8a r = (3 25T1/3 x10-8cm=1483x10-8cm
^
'c-27Rb f.4t3A or 14t.3 pm
=
r.. Iogr = 1
-l
Calculate the yar derWaal's constanfs ofthe Bas. _ 1 508L-l x 0.0821 Latm K mol-l x 293K
-
C
it to be sphericat. =37 06
N
P, = = 27 P"bz
_rx28+(100-.r)x44
Eives a
,f* 100
. ar*a#-4, =zt oe
=zzr. (!)'=:r"v3
Le. a= 3P"v!
or 16.r = 4400 - 3706 = 694
or x=694/16= 43 38
= 3 (45 6 atm) (o 0987 L mol-l)2 .. Mol% of CO =43 3a
=I333L2atmmol-2 and Mol % ofCO2 = 100 - 43 38 = 56'62.
Calculation of radiut of the gos molecule J Assumilg that dry sir contains 7070
l'rrrl.?,
lue of b per molecule N2 and 2l% ()2 by volume, calculate the density ofdry
air at 25"C aDd I atmospheric pressure. A.lso calculate
b 0.0329 x ld cm3 mol-1 the density of the moist air under the same corditions
NA 6.022 x 104 mol-l ifit has a relstive humidity of407o. The vapourpnessure
ofwater at 25'C is 23 76 mm.
= 5 46 x lo-a cm3
Sotutio& Calculation of density of dry air, Den-
4\n :. tn- 4b = -----T-
5-46 x lO-B sity ofair means the mass ofair per litre.
But b = cIn-
First let us converr I L (1000 cm3) of air at 25'C,
1 atm pressure to the volume at S.TP
=1365 x 10-B cm3
\
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STATES OF MATTER 2la3
Pr Vt PzYz No. of moles of N2 in the air (zN2)
-T.:-E-
cm3 atm x v2
=o3:#l?);r'-3 ,ex,o-2
I atm x 1000 1
29aK = Z'73K No. of molqs of 02 in thc air (zo2)
-
Calculation oldeNity of Eolst air
'*-q,, MHo
C
% Relatirc humidity
v*i
S
or (.s),f+f
IIT
P=
.. Partial pressure of H2O vapours
40 x 23.76 =1.5 x1.465 =2.19Eatm.
= ____fIE = ,,, ,. |'tu)l)L t 6 A spheicsl balloon of2l cEr diameter
As total pressure
is to be lilled with hydrogen at NTP frcm s c]rlinder
= 1 arm = 760 mm,
coDtsining the gas at 20 atrEosphere at 27'C If the
. . Pressure of N2 + 02 io the air cylilder can hold 2 E2 litrts of water, calculate the
=76O-9 5 =750.5 mm number of ballons thot cau be lilled up. (I.l.L l9E7)
As N2 alld 02 are present in the air in ihe rario of Solution. Volume of the balloon
79 : 21volume, 4 r 422 l2t\3
= T,r = i,
.. Partial pressure of N, x ;so s mrn = 7 " lT )
= ffi =,1851cm3
592.9 nm
and Partial pressure of Oz = 750 S - 529.9 = Volume of lhe cyliDdet = 2 &2lines = ?320 cm3
Pressure = 20 atm.,
157 6 mm lbmperature = 300 K
Apptying gas equation Pv = a RT ie. n = CoDverting this ro the volume at NTP
ff Pr Vt Pz Vz
No. of moles of H2O in thc air (r H2o)
-T, =-n-
_ (9 s/1&)armxlL mx282/J I xv2
0.0821 Latm K-l mol-t x 298 K we ger ---35_ = -773_
= 5.1 x 10-4 or Yz = 51324 ql .
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2/64 Pradeep's
When the pressure in the cylinder is reduc-€d to one No\r
atmosphere, no more H2willbe released and hence 2820 2NO + ..- Oz 2 NOz
of H2 will bc left in it Hence volume of H2 uscd in
Moles I .602 x 10-2 o.32 x 10 '
cm3
0
filling the balloons
before
= 51324--2820 cm3 = 485M cm3. reaction
Number of balloons lilled Moles I 602 x l0-2 0 o 32 x 10-2
= 48504/4851 = l0 after -2 xo.32x1o-2
The average velocity et T"t K and the reaction
most probable velocity at T"z K of CO2 ges is =0 429 x1O-2
9 0 x l0'cm sec-l. Calculstc the values ofT, and T2. Thus, molesof NO lefr = a 2q x to-3
(I.I.T 1990) Now T= 220K (Given),
Solution. Average velocity =0 9213 x R.M.S. v=2s9u*uJmr=o:sr
velocity
Applying gas equation, Pn6 V = n RT
=os2t3x€ .rNO---r
nRT
3xE.3x107xT, 0 0821 L atm K-l mol
'9xld=O.9213x
This on soMng gives R
tr
EE
Tl = 1691 K = 0.227 alE,
Problen 9. A gra bulb of I lltre cspoclty coDtains
AR
8as
9x1d= Il the rstlo ofthe DoEt proboblc thc root meoD
EpGed to
IA
This on soMng Sives Tz = 2147 K for th€sr moleculcs et this temperature. <I.I.T 199i)
I't,,1,!, nI At rooE teEPersturc' thc follorring solutioE. volume of gas = 1 litre = 10-3 m3
reection Soes to coDpletion
.... N2O1 Pressure = 7.57 x 103 Nm-2
2NO+Or
-2NO2 No. of mol€s of the gas
Dimcr N2Oa .t 2.6t K ls solld' A 250 rzl llosk and
= (2.o x 7o2r) / (6.02 x 1#) = 0.fi332
a lfl) zrl 0ask ore separattd by a stoP- cock At 3(n K'
Appbting PV = nRT
ihc nitric oxide ln the lsrBer ltssk ex.rts Prcssure of
1.053 atm and the smoller one coEtalns 02 rt O 7t9 (?.57 x 101 x 10-3 = 0 00332 x 8'314 xT
atm, Thc Ssses sre mircd by oPenhS th€ stoP.cock and or T = 274'25K
alter ahe end of the reactiotr, the nosks 8rc coolcd to 220
K. NeSlectinS the vapour presturt ofdlEer' llDd out th. Root Mean square spc"o = \4f
plEsure and coErlro6itlon ol the gas FEaining at 220
K. Assume gss6 bohave ldeally <l.l.T 1992)
Solutiotr. ForNO: Y =EO mL=O E L'
T=3{nKP=1053atm
,tm
=|--------.--E--
PV=fffiffi='r'06exr0
1.053 x0 25 = 49426.5 cm r-l
.. ano=ftf '
ForOr rV = 1002L = 0 1 L,T = 300K, #ffiffiffiffi =o.82(Given)
. 0789x01 - 32 xl0'-r'
,or=ffi=0 = o'82 x 49426'5 = 40529 7 cm s-r
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STATES OF MATTER 2165
Pnrtlem 10. A 4 r I molar mixture ofHe artd CH. i.e. P = l atm,V = 41q).5rn3,T = 300 K
is contained ina vcssel at20 bar pressure. Due to a hole
R = 0 082 dm3 atm K- l mot-r 1{iivenl
in the vessel the gas mlxture le{ks out. Whst is tbe
composition ofthe rDixture effusing out initially ? PV = nRT
(I.I.T 1994) i.e. (1 atm) (4190.s ,,r3)
Applying Graham's law of eftusion, = r x (0 082 x 19-3-l *-' mol-l) x (300 K)
",rn
4190 5
fHc fhis givcs n =
rcH. o.o82x10-sx300
t 70345 .5 moles
r'.€. He diffus€s two times faster than CH1. Weight of 170345.5 moles He
.. Molar ratio of He : CHl effusing out initially
tg = ear 'r tg
= 1'1o345.5 x
fi
=t:1 Ttltal weighr of the balloon filled with He
Problem lI.
An LPiG (liquefied petrcleuD gas) = r00 + 681 4 kg = 7t1.4 kE
cylirder weighs 14 t kg when eEptF Whetr full, it
weighs 29.0 k8 aDd shows E prEssure of2.5 atm. ID the Maximum wEight ofthe air that caD be displaced by
course of use rt 27qC, tbc eelSht of lhe tull cllitrder balloon to go up = Volumc x Dcnsity
reduced to 23 . 2 kg. FiDd out the volumc of the gas in =4190.5x12=5028.6kg
cubic Dett€s used up st thc norEal usagc couditionq .. Pay-load ie extra load that can be attached to
ond the linol pr€ssurc inElde the cflitrdeB AEsuEe LPG the balloon = 5028 6 - ?t1 .4 = 4247 2kg
to be n-butsne tf,lth normal bolliDg poiDt of (rC. I'atblut Ii The compcitlor ol tbe equilibriuE
(rJ.r 19%) mixture (Cl, ;+ 2Cl),which is athined at l20O'C is
!9!9!94, Decrease in the amourt of LPG R
determiDed by Eeesurlng ttc rate of efrusioE through
EE
a piD-hole. It is obs€rved that et 1.60 Dm Hg pressurc,
= 29.0 - 23.2 = 5.E kB
AR
Volume of 10O moles at 1 atm and 300 K weight ofKr = E4) (I.I.T 1e95)
N
=/H
IA
'lRT
P soEtien.ff
IIT
=
I Ulrn
x to-3 m = 2'463D't'
2463L = 2463
i.e. I 16= v#
Final pressure iNide the cylinder. As the or M.t, = 6f zfl
crlioder contains liquefied petroleum gas in equi- If.r moles of Cl2 dissociate at cquilibrium, theD
librium with its vapours, therefore so long as tempera-.
ture remains constant and some LPG is presenq Clz ir 2Cl
pressure will remaiD mostant. As the crlioder still con.
At. eqm. I -.r 2x
tains LPG = 23 2- 14.8 = 8 4 kg, pressure rnside the
cylinder will bo same ie. 2.5 stE. Average molecular mass of the mixture
P
or For ideal gas, Pv = n nf = ff nf or fr{ =
$
ffi=ffi P2 = l5o0 tPa
As the cylindor caIl withstaDd a pressure of ld Pa 0.5 c x o ot2 L alm K-l mol-l x 300 K
- latmxo.ll-
= 1d tla = 1o0O kPa, hencc tt w l blott uP.
Pnthlen 15.20 dm3 of SO2 difluec ttrough a = l23gmol-r
t'rohlen 18.llsingtan der Wsals equstion calcu.
porouE poilition ltr 60 s. I9hrt YoluEe ol Or eilt difilEe late the corstont t4'when fi{o moles ofa gas confrned in
undcr slmllrr c!trditions ln 3Ot? @oor*ce 1996) a four litre flask exerts s Pressure of 11 0 atmosphere
at a temperature of 30o K. The vatire of rD' is 0 05 lit
,-, = ?H+ =!0,',-r mol-l (I.LT, l99E)
ot 16= O or u=lr'14rlm3
C
*
uH. , = Pn. .fr-l or r'M; = 3 x r/U or Mx = 9 x28=252
,= ",% rr-;,. " "; Atomic mass of Xe = 131 a
T_
. . Mass of F atoms
= X2 - 131 = !2L tt
Aromic mass of F = 19 U
ot
]"oln=2"\ |
,H2=1584L=014tofH2 ... No. of F-atoms - 1?1 = u
'lhis equation is quadrati ln V Flence sibility factor) for one mole ol a van der Waols grs at
0'C ard 100 stD prcssure is foutrd to be O.S. Assuming
C
7. The densiry.-,
ofneon will bc tushe$ 13. A gas b€haves most like an ideal gas under coDdi-
ar
tiolN of
(a) sTP pfac,zatm f4) Iligh pressure aod low temperarure
(c) 273C,l atm (d) 273C,2 atm.
(r)iligh remperarure and high pressure
_l?).Low pressure and bigh temperarure
,,yy'furaing to *ineric theory of gases, # (d) I-ow pressure and low tempcreture.
molecule
(a) The pressure exened by tb€ gas is proportional
to the mean velocity of the molecule 14. Ifvapour dcnsiry of 02 and H2 are 16 and 1, then
(6) The pressure exertcd by rhe gas is proportional the ratio of rate of diffusion of H2 to that of dif_
to the root mean square vclocity of the molecule iusion of 02 is
(c) The rmt mean square velocity of the molecule
(a) t6 (b) U16
proponioDal to remperature
thversely
li,liThe mean ranslationat kinetic enerB/ of rhe J*$ (d) ll4- ,( ttrt t ro,t
' molecule is proportional to the aholute 15. Containers A B aDd C of equal volume contain
temperature. oxygcn, neon and methane respectively at the same
9. 1\t the sarDe tempcrature and pressure, which of R temperalure and pressure. The correcl. increasing
EE
order of their masses is
lhe following gas€s will have the highest kinetic
(a)A<B<C (r)B<c<A
AR
(c) CHa
.,16, Tcmpcrarure below which rhe gas does not obcy
N
tdealgas laws is
t \! t . lt \.r.t, tt, t, , '')l
IIT
having dcDsities pA and pB are relatcd ry the sx_ (d) 0.6 atm.
pression
Itt D@n (.li.lr.'l: irt)t
19. The ratio between the root mcan square velocity of (a) KEso = KF-N,
H2 at 50 K and that of02 at 800 K is
(D) KEco > reN2
(o) 4 (b)2
(d)114. \t.t t: te,6) (c) KE6e < KE1,
$r1
20. X ml oftl2 gas effuses through a bole in a mntainer (d) cannot be Fedicted unless the volumes of the
Sases are gNen.
(c.D.s.E. Mr.T 2oo0)
in 5 scconds. The time takeE for thc effusion of the
samc volume of the 8as spccif,ed bclow undcr iden' Dcnsiry ratio of 02 and H2 is 16 : 1. The ratio of
tical coDditioDs is their r.m.s. vrlocities will bc
(a) l0 s€conds : He {d}6'sccoorts : O, (o)4:l (b)1:16
(c) 25 semnds: Co (d) 55 s€conds: cO2' (c)1:4 (d) 16 : 1.
and B is Sivcn bY
pressure, ils finalvolume will b€
(a) 1rnlPs) (M6/Ms)l/2
C
',lt.
t,t.l.I Jl.,s.2000t
IA
1g(t 30. At oqc and one atm pressu re, a 8as oc{u Pies 10o cc'
IIT
^tt"11MstM,Jt/2
(d) (M^/MB) (PBlPar/2. If the pressure is increased to one and a half-time
and temperature is increased by one-third of ab-
(where P and M are tbe prqssurcs and molccular
solute temPerature, then final volume of tbe 8as
w€i8hts of gases A and B respectvely)' ' /. i / " " will b€
24. Which onc of the followint $atcmenlsts r4ong lot (a) 80 cc (6) 88.9 cc
gas€s ?
(c)66.1a, (d) 1m cc.
(a) Gas€s do not havc a definite shape and volume ( I).(' li.l; F: )t)0t)\
(6) Volume of the 8as is equal to tbe volumc of the
mnbiner confining the gas The deDsity of at ls 0 00130 8/ml. The vaPour
deDsity of air wi[ be
(c) Confined gas exens uniform Pr€sture on the
' ' wells of its contaiDer in all dire.ctions (a) 0 0006s (D) 0.65
uei8h' (c) 14 a816 (d) 14.s6.
-(/) Mass of the 8as canriot be determined by
ing a contaiDer in s'hich it b enclGed. il).(.E.D.E.2000|
t(' It \ i.: !'.\l I lt)I)lt\ 32. The retatioDshiP which des€ribes the variation of
vapour Pressure with temPerature is called
25.
(a) Hcss's law (r) Arrhenius equation
(c) Kirchoff's law
same temperature ? (D,Clausius-clapeyron equation. t 11. H. Li. 2 0 0 0 \
19. c 20. b 21. b 22. d 23. c 24. d 25. a 26, c 27, a 2t, c
29. d 30. D 31. d XZ,.l
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STATES OF MATTER
'2n1
33. DeDsities of two gases are in thc ratio 1 :2 and tbeir (a)Vd> 22 4tilIes (D) V,n < 22.4 titres
temperatures are in the ratio 2 ; 1, then the ratio of
thcir respective prcssures is (c) V- = 22 4 litres (d) V,' = C4 31;1r"..
(d)1.1 (b) t:2 ,t l 't )i,,
.{)2: t (d) 4: t. 11 t'. )o0o 40. At 100'C and 1 atm, ifrhe densiry oftiquid weter is
?tr4as equation PV = ,r RT is ob€ycd 1.0g cm-3 and that of water vapour is
(4) only isothermal process 0 m06g cm-3, then thevolume occupicd rywarcr
(r) only adiahatic process mol€cules in I litre ofsteam ai that temperature is
.@\6otn @) and (b) (a) 6 cm3 (6) 60 cm3
(d) None of these. (B.HU. 1000) (c) 0.6 crn3 (d) 0.06 CrI!3.
35. The rate of dimrsioD of a gas haviog molcc,rlar
t l.l l:2ht)tt
weightjustdoublc ofnilrogeD gas is 56 mlr-1. The 41. The root mean square wlocity of an ide3l g8s at
rate ofdiffirsion ofnirrogcD will bc constaDt prcssure \taries with dcnsity (d) as
(4) 79 l9 mlr-1 (b) 112 0 mls-l (o) d2 (b) d
(c) 56 mls-1 (d) 9O.O ml s-1. (c)'/t (d) 1 / ,td.
t(.1).1L1 J000 )
36. '[rc following graph illustrates 42. At whar tempe rarure will the RMS of SO2 be rhe
same as thar of 02 at 303 K ?
?
N
hibited by
(a) molecular nteraction between atoms and
S
RT >
N
PV/nRT < 1
(c) Pseudo solrds (c) finite size of the atoms and PV/,RT > 1
(d) Molecular solids (d) finite size of the atoms and PV/,RT < 1
46. d 47, d 4E, c 49. c 50. d Sl. b 52. c 53. , 54' a 55. a
56. d
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STATES OF MATTER 2173
(c) 24 (d) 36
59. According to Charles' law (one or more)
(a) (dY /dT)p=K (b) (dv /d\p= -K What is the pressure of 2 mole of NH3 at
(c) (dv / d1)p = -K/T (d)v aT.
27'C when its volume is 5 litre in van der Whals
eguation ? (s = 4 77,b = 0.03711)
60. The root mean square velocity of one mole of a (a) 10.33 atm (6)9 33 arm
monoatomic gas having molar mass M is Ur.m,, .
(c) 9.74 atm (d) 9.2 ar.rr,
The relation between (he average kineric energy
(E) of the gas and U' is
The ratio of most probable velocity to the avcrags
velocity is
(o) u'...,. (a)tt2 (b) 2t t
R
EE
(4 'li /2 (d)2/,ti
(D) u,.,,...
AR
/+ (c)1.2/x1dt (d)3 24 x te l
IA
As the temperature is rais€d from 20'C to 40'C, the Molar volume of CO2 is maimum at
average kinetic energy of neon atoms changes by a
factor ofwhich of the following ? (a) N.TP. (6) (rc 8trd 2 . 0 atm
(a) 12
(t+72Tcand 1 a.6 (d)273"Cand2atm
@'hB/293
JPrjt3ze3 (d)2 t.t.t.tr r. zLro,tt
iJeKc.L.r2l0t)
rtrhals equati .n of state of rhe gas law, Slope of tlte plot bctreen PV aod P at constaDt
6?. In yaD der
teEperature is
the mnstaDt , is a measure of
o (a) zerc (b) 1
(a) intermolecular repulsions
(c) tD (d) 1/,lz
(6) intcrmolerular attraction
tBtlLt. / .t; (, 1.: )t)011
,1relvolume occupied by the moleqrtes
(d) intermole{ular collisions per unit volume 7lJ The numeri@lvalue of N/a (where N is the nu mber
of molccules in a gil€n saDple of the gas and ,, is
(.t.t.t;.t:.E. )0ti4\ tbe number of moles ofthc gas) is
6e Containers A and B have same gas. pressure,
volume and temperature ofA are all twice tbat of -qtytla"rP
B. Then lbe ratio of the number of molecllles of A (d)166xlO-le
and B are
(a) 1 12 gfi'r I Kenla C.li.li. 200J i
A
57. a,b,c 5E. bd d,.I
59. 60. c 61, c 62. c 63. b 61. c 65. a 66, b
67. c 6E.c 69.c 10. a 71. b
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2174 ),t;t. rt')s Neut Coutsc Chemlxrg llftfl
72. N2 is found iD a litre flask under 100 k Pa prEssure ar( 4+,lltnicn of the following statemcnl about amor-
02 is found in another 3 litre flask under 3m & Pa
L/ phous solids is incorrect ?
"ir-..iE ;- ,:\/E
AR
xllr=
w/2 l/2
i7TTi7fi - 177+;nfi 'H, ./_vf
r3030 ls '.=YM;,
21632 16
Sases mntain
" +=E
'fhe equaluy holds good only for (b).
t
..Masses of 02, Ne and CH4willbe in the ratio Polar molecules (like H2O) have drpole mo-
32 i 201 16. meDt. As a result intermolecular forces of a!-
17, Prcssure of dry 8as, P = nRT
y'
traction are Sreatcr and so is the critical
= 0.016t x (0 0821 x 1000 760 rnlntm) t tcmpciature.
x 298 / 428 =130run
AAISLC'ERS
e 73.a 74.b 75. b
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2n5
STATES OF MATTER
23. rEPand d1/'ld or dl/'lPI. 37, Mass oI ?2 4 L of the gas at STP = Gram
Molecular mass.
Heme
+=+(#J"' u- A/3RT
v -Tr ,
24. Mass ot the gas rs determined by weiShiog the I (Hz) T (H:) M (Nz)
contaiDer containiDg the gas aDd theo the empty
conulner.
,rN;= M(q)ix'rNt'
ICE. ofa 8as depeDds only on temPerarure-
*+=+=q,=fr=,,0 Trtl^l
z=affix l+
or T(Nr-2T(H2)
nor=4/32= 1/8 mol,,H2 =2/zmol= ) rnol'
'lbtalz=9l8mol
ie. T(Nr>T(H2)
PV =nRTorP = zRTly'
or TGI, < T(Nz).
= (9,E) x (0 0821) (213)11 = 25 21s atm. z=ffi ie. ,ffi'.r
v1/ Tt =vz/'t2le.3oo / 3ffi = Yzt 2ao
or PV <nRT
or V2 = 280 ml or latmxv<lxO0E.21 x273
or V< 22'4lihca.
P
1Y 1 / -11= P 7Y2 / Tx R Mass of l L steam - 1000 x0 0006 =06t=
EE
i.e. (1 xloq/213 =(1 sxv)/(2'13+91) Mass of liquid w8ter. Vol. of Pater = 0 6 cc. Same
Vz = 88 9c.c.
steam.
C
v-BI= o o82-x373
= 30.58 L - 30.6 L.
5t. According to Boyle's law, PV = K at constant T 69. PV = RT or V = Greater rhe value of TE,
$.
.. P = KN or (dP/dv\ * -K/v7. greater ls thc volume.
ADDITIONAL UESTI
As se rti
o n - Re a e o n Ty p e Q.u e ons sli
rhe r"rroring q";ilons cotrEilt of t o stot",n*G p"r"u rr AlEcrdo' Etrd Resron, wbllc enuwcrlng
these questions you arc rlqulrld to cho(*. ary oDG ""*,
of thc follorlJlg llyc r6porr...
(a) If both Assertlon aDd RcaaoE orr truc sud thc Rlllor lE corrcct cxpl,rordon ol thc Arecrtlou
(r) If both AsrcrtioE aDd Rrsson rr! truc and the Rcr!'on is not thc coricct cxphnrdotr of ttc Alt rdott
(c) IfAssertlor ls true but thc Rroson b faka
(d) IfAs.sertion is falsc but th. Rcrsotr ls Eue.
(e) Il both AsrertloD ond Rcaaon arc fallc,
Assertion Reason
For a certain fxed amount ofgas, the producr PV Real gases deviate ftom ideal behaviour at lo pressure
is always constant. and high temperarures.
Different gases at the same conditions of tcmpera- AveraSe kinctic enerEr of a ta! is dirccly proportional to
ture and pressure have same root mcan square temperature h Ketvin scale.
velocity.
At zero degree KeMn the volume occupied by a gas All molecular motion cealcs at 0 trC
is negligible. R
EE
The pressure of real gas€s is less than the pressure Tbe intermolecular forc€s of attraclion in real gas€s are
ofthe ideal
AR
Latent hear of fusion of solid carbon diodde is SiO2 exists a! a discreie molecule.
N
Liqucfaction of H2 and He is difficult. Critical tcmperarures of tI2 and He gases arc high.
t. The value of van der \lbals constant ,c, is higber Intermolec.ular t ldrogen bonding is prcscnt in ammoDia.
for ammonia tban for nitrogen. (I.LT t99t)
Effusion rate of mygen is smaller than nitrogen. Molecular size of nitrogen is smaltcr than dygen.
(a.r.r.M.s. 2000
True/Falge etatements
Wich of the Io owing stotemefis @e labe ? Revrite 7. A liquid which has high coefficicDt of yiscGity has
them cotectly. lo$, fluidity.
The graph between PV vs. P at constant tempera- E. Glass po$esses fluidity.
ture is linear parallel to the pressure axis. 9. Crlstallioe soli6 are isotropic.
Volume remaining constant, pressure is invers€ty 10. ID a 8as, intermolestlar forcB of anraction are
proporlional to temperature iD degrees keMn. weakest whilc thermal encrry is bighest-
Real gases shop deviation from ideal behaviour at 11. In the van der Vrbal's equation
Iow temperature aDd high pressures.
Matchin7Ty?e Q.uesaiong
Lfatch thc cntrics of cohnu A with apopti* e*its ol cola,B B
columD A Column B
3. /H
C
1.one2. ld3. manometer 4. Lord KeMn s. -213'C 6.watet vaPours, temP€rature 7' Microscopic
model t. e.(ernal pressure (atmosPheric pressure) 9. reciProcal 10. crystallites 11.' Nm-2s
orPasorkgm-ls-1 rz.$rr. Poor 14' drrectly Proportionalto 15. glass.
MATCHING TYPE OUESTION S
1-z2-3,3-1,4-4.
z. a= /-j -L, M. so r depends not only ofl T but 9. Molecular size decreases from left to nght aloDg a
penod. Thus, molccular size of nitrogcn is Srealer
than oxygen.
3. \'ihratory motton cxists even at 0 K
7, Crrtical temperaturqi of Il2 and H€ gas€s 8r€ lo\x.
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[, NO UT
Atornic ?t?uctu?e
,,,.,,.'5-. -;E, ,., ;.,9,;:..,,.;
subatomic particlc.s
3.1. Subatiomic and Fundamenti-l Particles+:i
N
kC u
theory is usually given to ancient Greeks, a
landmark in the progress of chemistry took place Electron 1- 9.1(D39x10-31 0.000548596
with the advent of Dalton's atomic theory (dis- Proton 1+ 7.00727663
7-67262x1O-27
cussed in Unit 1).
Neutron 0 1.0086654
Dalton, a British school teacher, in 1808, 1.674/3xlo-27
proposed that matter was made up of extremely
small, indivisible particles called atoms (Greelg
One unit charge = 4.8fl298 x 10-10 e.s.u.
aloms meals'uncut-sble'). The concept continued or 1.6@10 x 10-le coulombs
to hold grounds for a number of years. However,
the researches done by various eminent scientists One u: lll}rhthe mass of 'l2C atom.
like J.J. Thomson, Goldstein, Rutherford, Chad- We shall now take up a systematic study of the
wick, Bohr and others in the later half of the 19th discovery of these fuudamental particles and other
century and in the beginning of the 20th century
have established, beyond doubt, that atom was not
related discoveries which have been made from
the smallest indivisible particle but had a complex time to time.
structure of its own and was made up of still smaller 3.2. Discovery of Electron-
particles like electrons, protons, neutrons etc. At Study of Calhodc Rays i
present, about 35 different subatomic particles are
known but the three particles namely electron, The electrical nature of matter had bcen indi-
proton and neutron are regarded as the fundamen- cated in very early experiments on the production
tal particles. of frictional electricity (i.e. rubbing of glass or
3^
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3t2
GAS AT
LOW PRESSURE
S
PUMP
ANODE
IIT
* lt may bc notcd lhat c,hcn thc gas prcssuE in thc tube is 1 arnosphcE, no clcctric currcnt flows rhrough the rubc. This is
bccause the grscs arc poor conduc-toi of clcctricity.
'.Thc tclcvision picturE tube ii s cathode ray tubc in$hich I picturc is prcduced due to fluorcscclce on thc telcvision screen
coated with stritablc material. Similarly, lluorcsccnt light tubcs arc also cathodc ra)6 tubes coated inside wilh suitable materials
which producevisiblc light on bcing hir with cathodc ray6
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ATOI.TIC STBUCTURE
3/3
(v) They cause ionization Thc charge, 1.60 x 10-1e coulombs, is rhc
of the gas througlt smallest measurable quantity of charge, and is
which they pass.
callcd onc uait. The mass, 9,11 x 10-28 g, is ncarly
(vi)
They prcd,uce Xroys when they s,ike 7/1.837th ol that oI hydrogen atom. This can be
against the surface of hord metals like rungsten, easily calculated as follows :
molybdenum etc.
1 g atom of hydrogen
(vii)
They produce green fluorescence on the
glass x,alls ol the discharge albe as $,ell as on cetlain = 1.00ljg= 6 02x 1023 atoms
other substances such as zinc sulphide. i.e. 6-02 x 1023 atoms of hydrogcn weigh
(viii) They affect the photogq,hic ptstes. = 1.008 C
(o)rn"y rhey
.. One atom of hydrogeo wcighs
can easily pass Th"i I . 008
are stopped on hick- = 6 a2, 16z:..-
c = l' 67 \ 10' 24
I
ness.
Mass of H atom 1.6'7 x 1o-24 o
From the study of the various properties, as
Mass o[ clectron = ,;t, , ,-r{ = ls::
explained above, the two most importint results
are: R
Using morc accuratc values, the ratio comes
EE
out to the nearly 1837.
(i) Cathode rays are made up of material
AR
particles. ed as follows:
(r'i) Cathodc rays carry negative charge. rlicle which
C
determine the exact charge and mass of the first produccd from the material ofthe cathodi aod
electrons. Tllyo types of experiments were carried tube due to
out. These were by the high
cathode.'
Electron is a universal constituent of matter.
AT Low PRESSUBE
N
platc
callcd
S
N
Partic
IA
BLOCK
MOST OF THE
c!-PARTICLES
C IRCU LAR STRIKE HERE
ZnS SCREEN
o
close to this positive bodY. nucleus in which the electrons were distributed.
N
oof
a
Thus, according to Rutherford's model of
atom, the atom consists of two Parts :
(i) Nucleus which is very small in size, carries
positivo charge and in which the entire mass of the
atom is concentrated.
th€ mdi us o[ th€ n uclcus
thectod fiediffercnce
isofth of about 5 km
in sizc
r.
No two clcmcnB hEvc thc 6ane atomic numbcl. Hcncc I proPeny of an clemcnt
chart
and is takcn as thc basis of classification of clcmcnts in thc Pcriodic
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ATOMIC STflUCTURE
3n
\__/:(J
G-'(/) \_,i
* o
o-particle Be-atom C-atom Nautron
Charge=+2 Alomic No.=4 Atomlc No.=6 Charge=0
than the actual mass of the atom. This Ied to the idea Mass=4u Mass=9u Mass=l2u Mals=1u
lhat therc must be somc other particlcs prescnt in the I|H" * lae ttc
-+ 3a
nucleus and that these particlei should be neutral but
should have considerable mass.
t( o
o-particle B-atom N{tom Neulron
Charge=+2 Atomic No.=s Atomic No.=7 Charge=O
Mass=4u Mass=11u Mass=l4u Mass=1u
t|H. . 'lB 'f r
* l,l
In view of the discovery of neutron,
Rutherford's model of atomwas modified. The only
modification was that the nucleus of the atom con-
tained not only protons but also neutrons.
(N.C.E.-II.T,)
IA
1- x = 6 .U2Z
x 10?3 molecules of NH,
= t.lix 10:5 10-r electrons
= (6.022 x t0a3) x (7 + 3) protons
= 1 .09E x 1027 electrons.
late the mass and chage
= 6.U2Zx l0 protons
of on N.C.E.R.i)
.'. 34 mgi.e. 0 .034 g NH,
Mass of one elcctron 6.022 x 7e4
_x
= tl 0.034
= 9' 11 x 10-3r kg
.'. Mass of one mole of electrons
= 1.2044 x ld2 protons.
= (9. 11 x 10-31) x 16.022 x tgz:; (D) Mass of one proton
= S.4E6 x r0-7 kC
x 10-27 kg
Charge on one electron
= 1.67'26
.'. Mass of 1.2044
x 1022 protons
= 1.602 x 10-19 coulomb = (7.6726 x 10-27) x G.Z\M x
. . Charge on one mole of electrons 7021) kg
FO".-,P,,R.AC.1trlCE
lac (Assume that the mass of
1, Calculatc thg total number ofelectrons present ln neutrons in 7 mg of
one mole of methaoe, neutron = 1 .6?5 x 10-27 kg) N.c.E RT)
(N.C.E.R.T) [ \rs 6 02z x 102]
[turs. (a) 2.,109 x rdl (r) 4 035 x 10-6 ktl
2. Find (a) the totalnumber and (b) the totalmass of
T 9 FoRotFFtcuvr ?e.oeLr*v,g
l. 1 molecule of CH1 mntains €lectrons z, 1 g atom cflaC - 14 g
=6+4=10 = 6 022 x 104 aioms
'. 1 mole ie. 6O22 x 1F moleculcs will coDtain =6 022tlOBx8neutrons.
electrons = 6.022 x 1024
can be known.
upoa tic number of Prototrs.
For example, if'Z representsthe atomic num-
ber of an element and 'A represents its mass num-
ber (or atomic mass rounded off to the nearest
whole number), then
No. of electrons = No. of Protons
- Atomic number (Z)
and No. of Protons + No. of neutrons
atom. This is called mass number. Hence = Mass number (A)
Mos nuaficr d'endefrr a 'No' alFobrt .'. No. of neutrons : Mass number (A)
+ ilo' d'Eutmns'
- Atomic number (Z)
The mass number of ar element is nearly e.g. (i) For sodium'
atomi
equal to the ever'
:
thq main differen tuT Atomic number (Z) 11
lH and nan:ed as protium, deurerium (D) and For example, o2-. F-, Na+, Mg2r, Al3+, Ne
N
\i)z: lZA = 3s(ii)z = e2,A = 233 Further, No. ofneutrons : Mass number
Similarly, volume of the atom But in the formation of calcium ion, two
elcctrous are lost from the extranuclear Part ac-
= k ln = AIt (lo-\3 n cmt cording to the equation Ca -r Ca2+ + 2e- but the
.. Fraction of the volume of atom occupied compoiition of the nucleus remains unchanged.
4 r7 110-13)3/3 cm3 _ .. No. ofelectrons in calcium ion
-- 20-2 : 18
by the oucleus 10_15
. (Given)
Mass No (A) = No of Protons
S
+No. of neutrons
IA
:7 +7 --'36-1:35
=L4
IIT
,lilx.1\1i'l,li 5.
Calculale the percentage of xx22+ (lW-x\?l - 2i.z
higher isotope of neon which hos atomic mass 20'2
100
oia tt itoiop"i nove the fiass numbet 20 aad 22' or22x+2100-2frx=2020
"
. SupPose zNe = xVo. or 2x=20
Then 2otle
= (100 - r) 70 ol x = lo i e. 22Ne = l07o
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ATOMIC STRUCTURE
3111
Hon, many nuclcons are present in an atom of Nobelium, t How many electrons are presenr in the
ffiNo
atom? Hou, marry nuclmos may be considered ss neutrons ?
3. Crmplete the fo[oying uble :
Particlc Atomic No. Mass No. No. ofelGctrons No. of protons No, o[ neutrons
Sodiumatom l1 t2
Aluminium ioo 27 10
Chloride ion 18 18
Phosphorus atom 31 l5
Cuprous ion
-
28 ;
4. Complcte the follof,ing table :
Name ol the portlcle Moss No. Atomlc No. Piotons No, of Electrcns Neutrons
Oxygeo 8 8
Sodium ion 23 R
l
EE
Bromine 35 45
AR
How many ncutrons and protoDs are there in the foltosring nuclei ?
N
(N.C.E.R.T.)
IIT
Nome of the parti(le Msss No. Atomic No. Protons No. of Electrons Neutrons
16 8 8 8 8
Oxygen
sodium ion 11 11 10 12
80 35 35 35 45
Bromine
s. (a) P - 13,e- = 1O,n -- 14 (b)p =8,e- = lO, n ='1.
6. See HiDts belolr.
R
EE
{tr;p1p,;: iU,R,K'N,O,WL
AR
q combination ofelementary
C
It is helieved lhat fundatnenlal particles likc protons and neutrons are made uP
ftactionalcharges and c€rtain
;;fti;;;r"d i;"[. it "i".i"r.nt"ry
S
lii:ii -1. The rest massofthe elecrron is 9.1095 x 10-31 kg. On the atomic scale, the rest mass of the elecron.=
IIT
0.0005486u.Itisthemasspossessedbytheelectronwhenit,ismovingwithavelocitymuchsmallerthanthe
p;: where c is
velocity of light. However, wheD it is moving with velocity l,, its mass is given bym = ,,/
I_ 1, r ciz
thevelociryofltsht.ThuswhentheeleclronismovingwiththevelocltyotliSht(sothaiU=c),itsma.ssisiofinite,
to the relation
r.rr.!r .l. The radius, r of the nucleus of an atom is related to its mass numb€r, A, according
, = Ro o"' where Ih is a c.onstant having value = t 4* 10-15 m'
iii:ir {. .Ihe
rad:us of the nucleus isofrhe order of t0-15 ra while that of the atom is of
the order of 10-10 rz. Thus
nuclear radius is 1/l0O,0O0th ofthe atomic radius'
,iiil 5. The volume of the nucleus is of the order of 10-45 rz3 while that of the atom is 10-I rz3. Thus volume of the
to atom'
nuclcus is 10-15 of Lhat of the aiom ie. nucleus is very small in size as compared
i:;:ii 6. 'Ihe radiiof the nucleiare usually expressed in terms of Fermis (1 Fermi = 10-13
gm = 16-15 ,;
The nuclear radii lie in the range of I 5 to 5 5 Ferml'
Iili 7. 11.," nr.,"u, nas uery trigtr i.e. tora gtcml lor t0l7 kgzz3 or 10t tonnes/cm3; which is about 1012
oe;ii
times that of lead.
ti'
9. n.
10. Moselcy in 1913 He found that wtlen cathode rals hit the
6 aharacteiislic of the element bombarded'
,:.ll.Thomsonwasawarded1966NobelprizelnPhysicswhileRutherfordwasawardedl90SNobelprizeln
chemistry for studies on chemNtry of radioactive substaDces
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ATOMIC STHUCTURE
3/13
'
,-11L.,,,.
:r'lllll-lit()r
. \ I' tr
(rd) The radiations possess wave character
and travel with the velocity of light (i.e. nearly
1 r R.\ \ r ol )t.t,
-.Y1t1_!i ''"rjir'.- 3 x ld m/sec).
.- -::-: ': "' =''''"' ' " .,''
"'''''t' Because of the above characteristics, the
It is observed radiations are called Electromagnetic radiations
teristic line spectra or Electromagnetic warcs.
not be erplained
. _.(rr) equire any material
nuclear model of atom. Itr order to understatrd line medlu-Ilr example, rays from
spectrum it is essential to understand the nature of the suo ce which is'a non-
light (or radiant energy) which in turn was ex- material
SoEe imlnrtart ctaracErlsdcs of a mve.
The main characteristics of a wave are its
wavelength (l), frequency (rz) and velocity (c).
atom sullered from a serious drawback. Hence a These are defined as follows :
new model of atom, ca.llcd Bofu,s model of atom
was put forward. This model of atom was able to
explain the drawback of Rutherford,s model of CREST<-7r-+CREST
atom and the main lhes of the hy&ogen spectrum.
Now we shall ta-ke up a brief discussion of the
above developments one by one.
3.10. Nature ol Electrornagnetic Radiation
(Electromagnetic Wave Theory) Hfl_,iffiffi R
EE
This theory was put forward by James Clark
AR
Maxwell in 1864. The main points of this theory are FIGURE 3.1 1 . Some characterrstics of a wave.
summed up as follows :
C
S
m or cm or nm (n4nofiEto) ot W biconater).
rudiant enetgt.
1 A = 10-8 cm = 10-10 m
ist ofelectricand mag_
netic ndicular to each othJr 1nm = 10-9 m, 1 pm : 19-12 p
and to the direction of Frequency a/a wave ir dcfined at tlu number of
propagation of the radiation (Fig. 3. t0) . wava past,l,g througft a polnt ifi ono second. It is
reptw ed by u (nu) and is *pressed in Hefiz (Itz)
Electric,leld or cyulzs/sec or simply srr- L s7 s-t .
component
1Hz = l cycle/sec
Yelcxlty of a vaw is defined as the lincar distance
traveltcd by lhc N,aye in onc second. It is reprc-
seucd by c ond k eqtressed in cmlscc ot
mlec (m s-t ).
Besides the above three characteristics, two
other characteristics of a wave are amplitude and
FIGURE. 3. 10. Radiaton colEidng of ekctic ard wavc number,
rnagn"tic flelds o-scilhting ln phnc. peryendi(llh,
lo each other and trolh perp.ndlcular to the dilPdlon
of propagDtlon. T}€y have same warelenglh, lrcquency,
speed and amphude.
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gl14 , Pradeep's
.c=vx1
INCREASING WAVE LENGTHS
o
um)
;INFRA
i 'iEU'
ULTRA; MICRO M.qIq
r.RAys X.RAYS vjb'rti i_ iiAVdE wAvES
'Bi+g' R
,(r'1) 106
EE
1 lolE \1 1
AR
C
ES.
,I(CREASI NG FREQUENCI
S
N
IA
l,(nm)
o
l,(nm)
,la l. Carcu late (a) wcve number and (D) Calculation of the FrequencY
I,lX AI tPt
(b ) freEte.ncy ol ye tlow rudiation s hav ing wavele ngth
FrequencY z : f
ol 5800 A.
Solution' (a) Calc,ulation ofthewavc number Substituting c =3 x 108 nilsec
Wave number (7) = 1/l and l:5800x 10-1om
But i = 58004 (Given) we get
= 5800 x 10-10 m 3 x 108 nr./scc
i=
-L ' = ssm ,. 1o=o .
"' 58oillo:ril; = 5.172 x 10r' sec-r or cycles/sec or Hz.
= l'72 x 16 m'1
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ATON,4IC STRUCTURE 3/15
"ROfiLEMg of
1' Calculatc the frequcncy ri
x tdnm- 1,,,. 10lrs-r1
havinS wavclength,3
infrared liatrons 5. Find rhe.frequency ofvisible light with wavelength
of5000A 1, 6x10t.sec:r1
6, Yello\p lighr emitted from a sodium lamp has a
2. Cllculate thc rangc^ of frequencies of visible light R
EE
from 3800 - 7600 A. waveleogth (r.) of580 nm- Calculate the frequency
Il (v) and the wave number (D of the yellow light.
[,\os. 3.95 x 10r' to 7.89 x l0l. s-
AR
3, How long would it take a radiowave of fregueDcy, [ 517 x lorts-r, 172 x 1o5n-1]
C
6 x ld sec-l ro travel from Mars to thc Earth, 7. Calculate the wavelength, frequency and wave
a
of a light wave whosc
S
number period is
x
N
distance of 8 km ? 107
2 0x 10-ros. (NC.E.R.I:.)
IA
=3x70-3m 3x108
,=!=3xto8rru-r=lonr-l = 2.66 x lG sec
" 3 x l0-r rz = 4 min. 26 sec:
2' ). = zeoo A 3800 x 10-l0rz 3.8 x
= = 10-7rz 4. e = 4 x 1ot1 llz (i.e. s'1).
c a x 108rru-1 vevenumuerr=|=|
"- i = ;ffi+;= 7.8e x 1014s-r
3.11. Limitaiions of Electrornagnetic Wave observing the amount ofcurrent flowing, the kinetic
Theory (Particle nalure ol electrornag energy oi the electrons can be determined.
radiation ; Planck's Ouanturn Theory)
Electromagnetic wave theory was successfirl in
explaiaing the properties of light such as interference,
diifractio-n etc. but it could not e':cplain the -J+
ohenomeua of 'Black body radiation', and
iPhotoelectric effee' which could be cxplaincd only if
e9
electromagtretic waves are supposed to harrc particle
nature. Each of thqse is briefly desoibed below :
(1) Black body rarlladon. If any substance
uli$ high 6slting point (e'g. an iron bar) is heated
it frrst Secomes ie4 tlen yellow and frnally besins FIGUHE 3.14. APParatue lor studying
to glow with white light' photoelectric elfect,
id However, the following three imPortant facts
tlu
are observed about the photoelectric effect :
(i) The electrons are ejected only iftheradia-
tion striking the surface of the metal has at least a
minimum fiequency (v6). If the frequency is less
of its intensity.
N
(ii) The eneryt ol each quantum is diectty (i) When lighr of somo particular frequency
propodionol to the frequency of the radiationr,i.e- falls on the surfac.e of metal, the photon gives its
Edv entire energy to the electron of the metal atom. The
electron will be dislodged or detachd from lhe
or
mstal atom only it the enerry of the photon is
where /r is a proportionality constant, called sufficient to overcome the force of attraction of the
Planck's constant. Its va.lue is approx equal to electron by
6'626xl0-u ergsec. or 6.626 x 10-sjoules sec. electrons are
(iii) The total anount of energ) emitted or ab- has a certain
sorbed by a body will be some whole numbet quanto. quency v).
Hence E: nhv (rI) If the frequency of the hcident tighr (v) is
where n is any integer. more than the threshold frequency(v), the excess
energy (hv -
ftvo) is imparted to the electron as
kinetic energy. i.e. K.E. of the ejected electron
= hv - hvoorlma, = h: - n o.
light of these views, Einstein in 1905 proposed that Hence greater is the frequency ofthe incident
ligit has dtal character light, grealer is the kinetic encrgy of the emitted
E phnedon of Black body radiadon and electron*'.
Photoelectric eltect
Explanation of Black Body Radiation. When R
EE
some solid substance is heated, ttre atoms of the
substance are set htooscillation and emit radiation
AR
C
S
REMEMBER
N
IA
. . in thc visiblc light, atviolct radirtioos havc rhodmum frEqucncy and thc rcd radiatiois
-'Thus (he
havE rhinimum fraquenc1,
t.d lish r. simitarry, rrc urrraviotc rigur hal uishc; hcrE/ rha! thc violc. risht and rhc i;fra;?
f:l:r.g:1":lT -.::]ryllT
ngnr na5 lcs5 c'lcrgf uratr clcn Ihc ted light.
.rlf of
kinctic cncrgr
- (Fi&
ploticd egdn t rh! fEqucncy of thc abrorbcd phorons, a straigfir tinc
oJ slopc ,,r is obtaincd i photoc[ctronc is ptoitcd against intcnsity of tr," in"io"ri-?iuti*
(kceping frcquency constant as shc,!*n in t{& 3.d (r)
to
lrF
Ft I
os I
".E-,I
Er
|!.{i$}.&f,ERHflA:t '-9ilt,purucx's
GUANTUM THEOHY
AND PHOTOELECTRIC EFFECT
v=5x10rasec-r l^r"=nu-hvo=h1r-uot
=6.625 x 10-x (5.2 x 1014 - 5.0 x 1011)
we get E = 6'6?5 x i:O-Y x 5 x 1011
= 6.625 x 10-x x o z x tora joules
=3 3125 x l0-l'Joules.
r IiXA,r\'ll'l,Ll 2. A 25 watt bulb emits = 1.325 x 10-20joules.
monochromalic yellow light of wavelengh of 0 57 EX.r$fPLlt r. A photon of wavelength
pm. Calculate lhe rate of emission ol quanta per .
x
4 10-7 m strikes on metol sutace, the wo* func-
second. (N.C.E.R.T)
Solutlon. Energy emitted by the bulb = 25
watt=25Js-l (... lwarr= tJs-r)
(i) EnergY of the Photon (E) : lrv
Encrry of one Pho roa (E) = hv = h * x (3x 1d)
hc. (6.6i26 x 10-34)
Here I = O'57 Pm = O'57 x 10-6 m ,{ 4x 10-'
(lPm=L0-6m) = 4'9? x 10-r' J
Putting c = 3 x ldms-1, 4.97 x lo-re -.
\,=3.l0eV
- 1.602 x 10-le " '
h = 6.62 x L0-31 J s, we g€t
(ii) Kinetic energy of (] lzr')
(3 x 1d ms-r)
- _ (6 62 x 10-s xJs)70-6 "-i..ion \z)
O'57 m =hv_hvo
= 3 48 x 10-1eJ = 3' 10 - 2'13 = 0'97 eY
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ATOMIC STRUCTURE 3/19
the maximum wavelength thqt teill cause a = 5.17 x 70-1 m = 5L7 x 7O-e m: 5l7nm
IIT
r\ \ 1e37xlo-rsJr
4. In the infrared region of rhe atomic specrrum of )i,:jffi;I*'ffi.:iJ;,".:;1";
e Light ofwaveiength 4 falls on the surface o?
bydrogen, a line is obtaiDed at 3802 cm - 1. c€lcu- cesium. cllculate the ener$r of the photo-electron
latc the enerry of rhis phoron (, = 6 .6 26 x l0 -34 J emitted. The crirical wavelength for photoelectric
sec). l,,i z.sO x to-aJl
etlect in casium is 6600 A.
OLEMS
1. E = Nltv =3 98x10 '-i.
101a v-l)
x 10-r Js) (4 x 7. 1 pm = 1O-17 m.Proc€ed as in $lved exampls 2.
= (6 .023 x 1021 (6.626
10. Electrons will be ejected ooly if the energy of inci-
= 159 6 x 103Jmol-l = 159 6Umol-l dent light is greater than the threshold eoerg/.
.1
2. E =rtv = h;. Thus E ( i Energy otthe incidenilight = h v = hc1
3.E=hv=hl
l)
- (6' 626 x to-x ) (3 x ldms-
--- Js R
EE
=
(10'?5 ,. io=i6a- = 4 97 x 1o-1e !.
rr. E=Nhv=Nhi
AR
=193?x10-l8J
C
r
N
= 494 5 kJ mol-l.
5, 1rua= lo-em 12.E=1eY= 1 609 x 10-1e J.
Proce€d as in solved examPle 2.
E=hv =hlorl =f
6 (i01= 0 50 x lo-lom,
(6 62 x 1o-s Js) Ox ld ms-l)
E=hv=hc7 - 1 602 x 10-1e J
16.626 x lo-31(3 x ld) , L
- = 72'40 x 1o-1 m = 12 40 x 703
0.50 x 10-lo
3.12. Study o, Emission and AbsorPtion Speclra the irBtrument is called a spectrograph and the
We have studied above that the electromag- P44ssaPh
record.ed on
of differcDt
a specuum
rumgnt used
icience dea
wavelengths
spectroscoPy.
a
The spectra are broadly classified into (i)
:: Emission spectra and (i) Absorption sPectra.
ns These are hriefly explained below : -
with the human eye. However, if in a spoctroscope, 1. Emission spectra. When the radiation
the telescope is replaced by a photographic hlm, emitted from some source e.g. from the sun or by
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ATOMIC STRUCTURE 3121
PHOTOGRAPHIC
PLATE ments. For example, sodium always gives two
S
It may be noted that on passing though the are described as their finger pinrs differing
prism, red colour with the lougest wavelengtb is from each other like the frnger prints of the
deviated least while violet colour with shortest human beingsr.
wavelength is deviated the most. Further, it will be discussed later that the
(n) Lhe spectra When some volatile salt (e.g., line result ofabsorptiotr
sodium clrloride) is placed in lhe Bu$en llame and of energy by the
(Fig. 3.17a) or an electric discharge is passed elec oms of the element.
througb a gas at low pressdre (Frg. 3.17b), light is Hencalhe line spectrum is also called atomic
spectrum.
. 2. Absorption spectra When white light from
any source is first passbd though the solution or
vapours of a chenical substance and then analped
by the spectroscope, it is obsenred that some dark
lines are obtained G the otherwise continuous
PHOTOGRAPHIC spectrum (Fig.3.18). These dark lines are sup-
BURNER PLATE
posed to result from the fact that when white figlt
LINES
(cont,i"i"g radiations of many wavelenghsf is
FIGURE 3.17(a). Line spectrum produced frorn passed through the chemical substance, radiations
a volatile salt placed in 6 flame.
I
Vrl
G
B
NaCl I
The names of these series and the regions in which
SOLUT ION they are found to lie are given in the Fig. 3.18.
sLlr PHOTOGMPHIC The wavelengths of different lines in each of
PLAT E
these series are given in Thble 3.2.
FTGURE 9.18. Producilon of absorPtlon sPectrum ' 'i',Uii;t-'-i.t.'rl',i;i;iirltlii ii; ;ili ;i'
lirIir)us lines in thc different serics
, dependirg
same place
her it is ob- LYMAN
SERIES
BAL.
MER CHEN
PAS. -;rr
nnr.cx- I
I
PFI,]ND
SERIES
where coloured lines are obtained in the emission SERIES SERIES SERIES I
ancs. This shows that the 121.6 656.3 1875.1 4050.0 7451.O
re samo as were emitted 1u2.6 486. I 1281.8 2630.0 4652.O
The sPectrum thus ob-
91 .3 434.0 1093.8 2166.0 3'.140.o
tained is, therefore, cal7r,d'absorption spectrum'. .0
95 470.2 1005.0 1945.0
Dllfer.ence bctween emisslon sPectra and 8b-
sorptlon slrcctra. The mail points of difference
93.8 3n.o 954.6
between emission and absorption sPectra are 93.1 388.9
summed up in the table below R
92.6 383.5
EE
:
SPECTRUM SPECTRUM
C
Absorption spectrum
Ls obtained whon the
S
transmitrcd liSht is
@) of the lioes by the rormula 7= - (+ - + )
analys€d
spectroscoPe.
in the ('i ni
)
It coDshts of bright It consists of dark where R is a constant, called Rydberg constanttt
coloured lines lines in the otherwise and has a value equal to 109,677 cm-l o.
sepsrated by dark conti[uous sPcctrum.
1 097 x 101 m-1, n, ard n2 are whole numbers
spaes.
Emission spectrum Absorptio[ sPecrrum and for a particular series z1 is constant and n2
cao bo continuous is al$,ays discon- varies. For example,
spectrum (ifsource tinuous sPectrum For Ll,rnanseries, nr = l,nz = 2,3,4....
emirs white light) consistilg of dark
or discontinuous lines. For Balmer series, n, = 2, n, = 3' 4' 5. ...
lioe spectrum if
r'.e.
For Pascheu series n1 = 3,n, = 4,5'6."--
sourc& emits somg
coloured radiatioD. For Brackett series n, -- 4,n, : 5'6"1.".."
The above expressioo is called Rydberg !or- When n, = 2, the expression given above is
mula.
called Balmer's lormzlz as it was frst put forward
For H-like particles, the formula is by Balmer in 1885 to erglain the seiies of lines
t = * [+ - \) ,' when Z is rhe aromic num- bearirg his name (i.e. lines in the visible region).
ri ";)
ber of the HJike particle.
Limitil
series in the
r, in the Ryd
l'.x {\l I'l.l'l 1. Calculste the ftequency and the oI the frnt line
R
EE
Calculste the
limiting line in
AR
C
rg's formula
(Rydbery constant = 109,677cm-1) _ 1 _(t
S
v =T= R
,.,
N
, = * f+ - + )
IIT
= x I -r = j=n
'9
[+ a =. (i-+)
109,677 cm 9749O.i cm-l
"1r
A=; = 9.,4q, t
: 103 x 10-e
cm = 103
m = 103 nm
x t0-7 cm =*,*=1*
Dividing (i) by (ri), we get
. (,,
c
t=-=,{ 3 x 108ms-l
'--'-
103 x l0-e m --2.91 x l0lss-l *= *x f o,r : 485.e m
7 nz=3
=5 x4 or l=364'4nm
6fiJ6
AltErradYety first calcualte R from (i) and
. ]=n (*- ,4),'
substitute in (ii) and (iii). For L?+ , Z
wovekn-gth..oJ the
frum ol Lt' ' ,on
etween two levels
whose swn is 1and. the difretence is z
Suppose the transition takes plac€
be nl andnr. =l@677x8cm-r
Thenn, *n, = 4andnz- nt=2 or t = *fi , 1'14 x 10-5 cm.
rcn=
1. What is the waveleDgth of the liSht emitted Bhen 2. Calculate theuavelength from the Balmet formula
the electro[ in a hydrogen atom undergoes transi- when n = 3. [,rrs 656 nml
tion from aD ener$I level with a = 4 to an ener$/ 3. Calculate the wavelengtb of the spectral tine in
levelwithn = 2 ? What is the mlour mrrespo[ding Lyman series corresponding to n2 = 3-
R
to this wavelength (Rydb€rg constant = 109,677
? nnl
lturs.102'6
EE
cm-l ) (N.C.E.R.T) [,trrs 4E6 nm, Bluel
AR
HINT,6
C
S
N
1s232 9 crlt''
IIT
its of thc
S
cle * ?-n4ne'
N
"
IA
.","i*8,--Rx(#) *.0
2t.a
" to-191 For H-tike partictes, en= -2"'T,T"o i." u""i-2
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l'radeep's
3126
RADIATION
OF FREQU ENCY
RADIATION
OF F REQU EN CY
IIT
the electron becomes less and less. This explains subjected to electric discharge or high tempera-
ture, an electron in the atom may jump from the
C
ionized state is taken as zero. When electron is the electron in the excited state is short, it returns
IIT
addedup into theion, attraction takesplace, energy to some lower energy level or even to the ground
it was abeady zerc, hence it be-
is released. Since state in one or more jumps. During each suchjump,
comes negative. energy is emitted in the form ofa photon oflight of
a dcfinite wavelenglh or frequency.
3. Quantization of Electronic EnerE/
Key Concept ofBohr's Theory. The most important
- The
The frequency (r,) of the photon of light thus
postulate of Bohr's theory is the concept of quan- emitted depends upon the energy difference ofthe
tization of electronic energy. By quantization we two energy levels concerned and is given by the
mean that a quantity cannot change gradually and
expression, Q -E, = fiy s1 y =
E-Er
continuously to have any arbitrary value but chan-
ges only abruptly aod discontinuously to have cer- where E2 is the energy of higher energy level and
tain definite or discrete values. To understand the
E1 is the energy of the lower energy level and h is
concept ofquantization, let us consider ar interest-
ing example. When we travel in a taxi, we find that the Planck's constant.
the pointer of the speedometer of the taxi moves Now, frequency is related to the wavelength
gradually and continuously since the speed of the :
asv c/7 where c is the velocity of light.
taxi can have any arbitrary value depending upon
the acceleration. On the other hand, the fare miter
E-Et
only moves abruptly and discontinuously ia multi
ples ofone rupee. This is due to the rcason that thc .hc
fare meter has been designed to have only certain " %-E'
tAt inlinitc distancc, thc clcctto, is considcrcd ss a ffte electron at rcst, wherE
its cncrry is talcn as zero. The enerE/ of rhe
electron in an atom is lower than thc cncrry of flcc elcctrons at rest. Hcncc it is ncgativc.
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3128
Corresponding to the lrequcncy or wavc- Thus different excited electrons adopt dif-
length of each p ine [erent routes to return to various lower energy
in the spectrum ht) lcvels or thc ground state. As a result, they emit
of the spectral of dilfercnt amounts of energies and thus produce a
above equations are found to be in got)d agrcement large number of lines in the atomic spcctrum oI
with the experimental values. Thus Bohr's theory hydrogen.
elegantly explains the line spectrum of hydrogen For example, when the electron jumps from
and hydrogen like Particles (like encrgy levels higher than n = 7, i.e., n = 2, 3, 4, 5,
He+,Liz+,Be3+,etc.) 6.....etc. to n : I energy level, the group of lines
5. Simultaneous appearance of a large num- produced is called Lyman seies.These lines lic in
ber oflines in the hydrog€n spectrum. Although an lhe u raviolet region,
atom of hydrogen contai.ns only one electron, yet its Similarly, the group of lines produced whcn
atomic spectrum consists ofa large nurnber of lines elcctron jumps from 3rd, 4th, 5th or any highcr
which have been grouped into five series, i.c., energy level to 2nd energy level, is called Balmer
Lyman, Balmer, Paschen, Brackett and Pfund. This series. Tbese lines lie io the isible region.
may be explained as follows : In a similar way, Pasc,hen series is obtained by
Any given sample of hydrogen gas contains a the electronic jumps from 4th, 5th or any higher
samplc is energy level to the 3rd energy level. Similarly, z.
ctric dis- Brackett series results from electronic transitions
from 5th, 6th or any higher energy level to the 4th
:''l;::l: energy level. Laslly, the Pfund seies originates by
hydrogen atoms absorb different amounts of ener- electronicjumps from 6th, 7th or any higher energy
gies and arc excited to different en€rg5r levels. For R
level to 5th energy level. The spectral lines of the
EE
example, the electrons insomc atoms are excited to last three series lie it lhe infrared region.
AR
return to some lower energy level or even to [he Paschen seires : From n : 4, 5, 6 ........ to tt = 3
IA
ground state in one or more jumps. The various Brackett seies : From n = 5,6,7 ........ ton : 4
IIT
\=a
B RACKETT
SERIES
PASCH
S ERIES
( IN FRARED)
BALIV ER
SERIES
(vrsrBLE)
SERIES
(U LTRAVIO LET)
model of atom. Accordi.ug to Bohls model of atorn, or = 0 - 1312 kJ mol-r)= * 1312 kJ mol-r
S
the electrons move along certah circular paths in one For HJike particles,
N
21.8
well established that the atom is three dimensional }jn= - ----T::- Z. ) atom-1
IIT
1a 61375 v 16-tr r;
in rtr$ Bohr orbil of,hydrcgen atom. Given that
the
Bohr radius = 0' 529 A,
= 4.863 x 10-7 m = 4853 A (or 4E63 nm)
Planck's constant, h = 6'626 x t|-Y Is'
It lies in the visible region.
moss o! electron = 9' l1 \ 10-3t kg and
-. I.lxANlPLf'l 2.How much energ) is required to I = t kgm2s-Z.
t
ionise a hydrogen atom if the electrcn occupies ftfth
orbit ? Compare your answer with tlu ionisation
nh Or U:- nh
mVr='.-
energt of tryd.rogen atom i.e. lhe enetg) requied to 21t -' - Znmt
remove the electron frcm fr.'Il| orbit. (N.C.E'R.T,) (l) (6 626 x 10-14 Js)
- zrz.u, R (9 11 x 10-3rkg) x 10 529 x 10-r0rz)
EE
- x 10-rq Jatom-l
2l'8-lr'"
En=---
= 2. 188 x ld Js kg-t ,,l-r
AR
.. ae = E: - Er = - 21.8 x lo-re l+ - +)
rt
,,i) Hence u =2189x 106ms-l
N
IA
IIT
!) AsE= hv
l will be maximum orr is minimum (r =
S
_ (6 626 x 10-27 x
N
2 09 x 10-11ergs
-r l/1 - 1)
IIT
I = ros.' rzz .m
\2' 3') = 9.51 x 10-6 cm = 951 x to-E cm = 951 A
I . Humphrey scries. This is another series of spectral lines which has b€en reF,orted. It is produc.€d when the
electron in rhe hydrogen arom jumps ftom outer shells to 6th shell re. for these lines
. (nz-nt)Vz-\ + l)
unes PrOOuCeq =
,l. --'T--.orbits was extended by Sommerteld by introduciDg tbe conc€pt of elliptical orbits.
Bohr's model ofqrcular
This belped to explain the fine lines ofthc atomic spectra.
I In any spectral series oftbe hydrogen specrrum, rhe intensity of line decreases as n2 increases.
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,ttt L' Lt
t" s Neq, Course Chem istrttfiti[)
.\DD IO YOUR Kl'laJ!vLEDGE Col'{aD
iiiil s. The Edius of the nrst Boh/s orbii b 0 529A(52 9pm).
Theradiusof,thorbitofH-atomie.rr-0.529xn2(A).Puttiogn=l,2,3,4ald5theradiiofthefirstfive
orbits of H-atom are given beloq:
Orbit(n) 1 2 3 45
Radius (A) o 529 2.116 4.761 8 464 13.225
similarly, for H-like particles (e.& He+, Liz+ etc.), ,^=o 529-"2 A.
, r, VelGity of ao electroo in any orbit of the H-like particle is related to the radius of the orbit as
"='l* *."-i
Bafmer seriescontains four important lnes whGe wavelengths are 6563 A 'a 62 A,4341Aand 4102 A rhese
[From eqn. (r), page 3/61]
' 7
are rcspectively called Ha, Hp, H7 and Hd lines. They are obtained as a rcsult of jump ftom = 3, 4, 5 and 6
'l
resPectively to z= 2.
spectra of hydrogen and hydrogen like particles have duAl chsract He derived thai if any particle
of mass nr' is moving with a velocity u, the
S
suffered a scrious blow with the advent of de wavelength associated with the moving particle is
IA
i For mor€ details, rcad mattcr given in thc shadcd bsckground on pagE 3ly and 3135.
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ATOI\iIIC STRUCTURE
3/33
unccrtainty in position and A p is the uncertainty in
momontum, thcir product is always constant and
n.'fhus A-r x Lp =n/qn
cqual to h,/4
In the light of uncertainty principle, Bohr
model of atom lostulating that clectrons move
along definite circular paths and hence thcir posi-
tion and momcntum could be deterrnined with ab-
solutc accuracybccame unacceptable. Now we can
speak of only in terms of'probability' of finding thc
clcctron a[ any particular position about thc
nucleus at any instant of time,
Kceping in view the wave naturc of elcctron
and the uncertainty principle, the movement of the FIGURE 3.24. the ontg
clectron around the nucleus is likc that of a bee electron olthe undarv'
around the hive. Sometimes it may come close to surlace for m nsilV
thc nucleus and sometimes it may move away from
it. Further it does not move inone plare (as wrongly It is clear from the picture that most of the
postulated by Bohr) but moves iu all directions and dots lie at a certain distance from the nucleus on all
in all planes around the nucleus. sides. Since the probability offinding an electron is
directly proportional to the intensity ofdots, thcrc-
The concept of'probability' may be under-
fore, the electron spends most of its time in the
stood u/ith the help of the following simple ex-
amplos: volume ofsphere bounded by that distance an(l for
rest of the time, the elcctron can be found ouisidc
(i) Suppose on a particular day, there are
R
the rrolume of this sphere.
EE
clouds in the sky. We predict that therc is achance
that it may rain. However, there is no certainty that Tle rcgion ol spae aroand. thp nuclcus which
AR
.
it would definitely rain because the clouds may d*riha thc probabihty qf fudiA cn elearon o!
rlisappear. This is expressed by salng that there is giwn ensg in kmt ol dals is called an elaclron
C
(ii) In
a game of chess, a better player has a
Nowhere is the probability o[ finding an
IA
ORRIT ORBITAL
t. An orbit is; wcn defined circular path around the T-E dECiE tlree 0rmensrional sPace around the
ttre
nucleus iD which the electrons revolve. nucleus within which the Probability of finding a[l
electroo is maximum QrPtogOEo).
2. It represents the planar motion of aD electroD 2. lt represeots the three dimensional modon of aD
ener-
. The
it did not take into account the concept ofdual
C
lunc-
naturc of matter and Heisenberg's unc€rtainty
S
in an
principle. Hence a new branch of science
N
#Ihe values of E and ty' are called .l8cn vrlu.s and.lgcr funcllons'
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ATOMIC STRUCTURE 3/35
based on Schrodinger wave equation. The im. 4. By firding rlrz at. different points around the
portant features of this model are as follows :
nucleus in an atom, we can predict the region o[
l. The electrons in an atom have only quantized space around the nucleus within which the prob-
values of energy. ability offinding the electron with a definite valuc
of energy is maximum. ThLs space around the
2. These quantizedvalues of energy are obtained nucleus is called orbital. That is wave function
from tle solution ofSchrodinger wave equation.
The corresponding values of the wave function V is callld orbitql wave lunction or simply atontic
orbital.
rp are also obtatled from the solution of
Schrodinger wave equation. 5. Since an electron can have many wave func-
tions, therefore, there are many atomic orbitals
3. The wave function g is simply a function of co- in an atom,
ordinates of the electron and has no physical
significance as such. However, 92 gives the prob- g contains all the
6. Ttre orbital wave function
ability of finding the electron at that point i.e. information about an electton in an atom and
electron density at that point. The concept of quantum mechanics helps to extract this infor-
probability is justified in view of Heisenberg's matlon.
uncertainty principle.
E967 A.
nn)
S
FOR;F 0 \ iE-,,
l "RODLEMS l0-5Js). 1
a
What will be the wDvel€ngth of a ball of mass 0.1
kg moriDg with a velocity of l0 ms-l ?
electron =
ft -6.6 x
9.1-I lo-31 kg Planck's constant
. 7.2Sxl0-1 nl
I r\ns.6.626 x l0-rzr]
3, Calcllate de Brogiewawlength ofan electron rhat
2. A moving etectron has 4.55 x l0-5 Joules of bas b€en accclerated ftom rest tbrough a poteorial
kinetic enerry. Calqrlate its wavelelgtb (msss of diffetnoe of I kV
[Ans 3.E7 x l0-rr nr]
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3/36
' Net4 Course Chemistrallfi[)
,"1 'ner+tt
R
ostal address of
EE
a person. Toknowabout a particular person, Mr X, Note $at orbital angular momentum depends
z'
AR
wc shouki know about his country iJtown, hislane only on ttre value of ''' and uot Thus all
number. J-orbitals (/ = 0),.e. 1s, 2s, 3s etc have orbital
C
and housc
rhe briefly 3l5iI;r,Iffi:1f1il,.(;i"51:?r!{r',.;r;ri
S
described below: -
have o.bit"l aogutai momentum
IA
present within the same main shell are found to be arrows pointing thc oppositc dircclion i.c
and
in the order s < p < d < f 1 ,1. .
C
I
which take up different orientations utrder the in-
fluence of the external magnetic field. The mag- FIGURE 3.26. Spinning of etectrons.
netic quantum number tells the number 6f
orientat This quantum number holps to cxplain tho
Same su magnetic properties of the substances. A spinning
the num electron behaves like a micromagnet with a definitc
shell (as magnetic moment. If
an orbital contains two
For a given value of ( rn can have values from electrons, the two magnctic moments opposs and
-/to + / including'0'. Thus cancel each other.
_ For s-sub-shell, / : 0. Hence rn = 0 (only one
value) i.e. s-sub-shell has
Thus in an atom, if all thc orbitals are fullv
only one orieniation or hlled. net mag[etic momcnt is zcro.anrJ thc subi
has only one orbital. stance is diomugncric (i.e. repcllcd by the extcrnal
magneric field). However, if iomc hsif- fillcd orbi-
tals are present, the substance has a net magnotic
momenl atrd is paramagnetic (i.e. altractcd hy lhc
external magnetic field).
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3/38
Neqr course chcm irtrgffri[
Idea ofstclls, subshells and orbitals. Tb sum up
R (Five 3dorbitals)
EE
-L-------
h- 3\ ,'
_::---:!-i----1 30
AR
(One 3s orbital)
S
N
(Three 2p orbitals)
IA
-4--------
IIT
(n = 1) ls /Ona I s
^rb'tal\
(K-shell) Subshells
IiX,C"MPI-E l. An ,lrrwn is in a 4l orbitat, For each value of rz, Oe spia quantun trum-
What possible vahtes Ior the Etantum numbe4, n' l, ber, s has two values, i.e', s = +I.f}aads= -U2'
. EIAtrIPLE 2. Wite down ahe Eta,tum nutn-
m atd s con it h@e ?
Since the electron is in a 4f orbital, bers n, I ond m for the following orbials :
the value of the principal quartum number,n = 4' i d? - rz (ii) 4 d S (iii) 3 d,, (iv) 4 d,,
(i)
For the f-orbital, the secondary quantum (v)2p"(i)sp,
number, I= 3. (i)n :3,1 = 2,m = -2 ot +2
The values of the magBetic quantum (m) are (iln:a,t:\m=0
.-l to +l including zero' Therefore, whelnl = 3,-m
has seven values i.J' -3, -2, -1,0, +1, +2and3'
(iii) n = t,l = \m = -2 or * 2
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ATOI\.4IC STRUCTUBE
3/39
(iv) n = 4,1 :2,m = -1or + t (ii) This sct oIquantum numbers is permitted.
(v) n :2,1 : 7,m = 0 (li)
This sct of quantum numbers is aot per-
(vi) n = 3,1 : 7,m = - 1or -i- 1 mittcd bccause thc value of spin quantum number
EXA.I\IPLE 3. What dcsignation is iven to an canlot bc zcro.
orbital having (i) n = 2, l:1, (ii) n =.1,t = 0, (rv) This set of quanorm numbsrs is also not
(iii) n = l:3and(iv)n = 4, 1:2?
5, permitted since the value of ,rz, cannot be greater
(i) n : 2,1 : 1 means 2p-orbital than 1.
1 AEzLIE,MISiF,OR R
1P-ffiC, E
EE
l. Ifn
AR
is equal to 3, what are the valucs of quantum (i)n - 1,1= O,m = O;(ii)n = 2,1= t,m
numberslandm? ard(iii)n=3,1=2,m=+t =-1
C
(subshelland (Orbitals)
C
its desigration)
(") (m) (s)
S
(t)
N
IA
l1
+2,-2
IIT
K 0 (1r)
1 1l .'
L 0 (2r)
t (2p) '2'
1
_,I
-1
0 '2'
1
-z 1
+1 *z' 1 1
1 rl )
M 0 (3o) '2', 2,-
| (3p)
-1
1
'2', 'l
0 +i, 1
+l 1
'2', iI
Conrd. on rrcrt Wge-..
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ATOMIC STRUCTURE
--2 a- 11
'2' -- 2
11
-1 '2', 2
!- _-
11
0 '2' 2
+1 4- 1i _-
' 2' 2
+2 .1 I
'2' 2
N 0 (as) 11
'2' 2
| (1p) +- 11
-1 '2' -_ 2
11
'2' 2
+1 4- 11__
'z', 2
2(M) .l I
-2 '2' 2
11 R
-1
f
'2', _-
EE
-
2
.1 1
AR
'2' 2
11
C
+1 '2',
!- _-
2
S
N
+2 .1 1
'2'
IA
2
IIT
11
3 (4f)
-3 'z', 2
11
-2 ' 2' 2
J- _-
11
-1 '2', 2
11
f
' 2' 2 -
__
32
+1 11
'2' 2
+2 11
'2' 2
+- 11_-
+3 'z', 2
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3142
Pradeep's
Whent = n, the orbit becoffes circular. R.lrtherk canDot be zero becaus€ that means miDor axis iszerowhich
in turn implics linear motion of ttle el€ctron passing through the nucleus'
ifid 4. Theshapeofanorbitalistheboundaryorco[toursurfacrdiaSramobtainedbyjoiniDsthePointsofcqual
oD wbich the probability
protaOitity 1,72; ot tle electron around the nucleus. In other words, it is the surfac€
that encloses the region within which the
deosiw r.i,lt is constant. Many such surfaces are possible but the one
pi"i"Li,ryG n"oi"gihe electron is very bigh, siy upto 907', gives the shaPe and size ofthe orbital'
ilil 5. The surface on which ?2 is coostant, ry' is also constant on that su rfac€. Hence
boundary surfaces for 'p2 an<l
'/
are identical. R
EE
AR
in shape.
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ATOMIC STRUCTURE 3143
\rithin it. Similarly,3s has twonodes.In general, any p-orbitals become largcr in size and have higher
ns orb_lafbas (n- l) trodes. energies. However, the thres p-orbitals belonging
/61 tne size and energy of the s-orbital in- tg a p4rlicular ggg-rgaleveltrare.equal energies and
ofpases as the principal quantum numbcr n in- 3rc called degenerate orbitals. Further whereas fu
cieascs i.e. the sizc and energy of s-orbital increases orbital has no node, 3p has onc node, 4p has two
in the order 1s < 2s < 3s.... nodes aud so on. Thus, we may conclude that
Shapes of p-orbitals. Ou the basis of prob-
ability calculations, it is found that the probability
Number of nodes in any_orbitql.= (n - /- 1).
of finding the p-electrons is maximum in two lobes Note.1. The formula given above is for finding
on the opposite sides of the nucleus. This gives rise the number of sphericaVradial nodes only. It is
to a dumb-bell shape for the p-orbital (Fig. 3.28). interesting to point out that whereas.r-orbitals have
spherical nodes only,p and d-orbitals have spheri-
cal as well as planar nodes. For examplc, @ orbital
has one nodal plane passing through the nucleus at
the origia. Similarly d-orbitals have two nodal
planes. The number of spherical nodes depends
upon th€ value ofn.
Thus tle above results may be generalized as
follows :
However, it may be noted that the probabi.lity of ;. Ibrill tunifudlrtuLt W ?{!iP 4 n- * ti'
C
Iobes ofp-orbitals
nucleus on which the probability of finding the
IA
maximum along the X-axis, Y-axis and Z-axis It has already been discussed that the dif-
respectively (Fig. 3.29). ferent subshells of the same main shell have dif-
ferent energies. However this is true only h case of
multi-electron aronr as shown in Fig. 3.30(b). In
case of hydrogen or hydrogen-like particles (con-
taining one electrotr only), they have the same ener-
gy as shown in Fig.3.30(a). In othcr words, it rnay
be concluded that rvi eruas ene@es of difrerent orbi-
I tals of hydmgen and lry&ogen likc panicles depend
Py upon the value of principal qusntum numbet (n)
FIGIJRE 3.29. Ditrerent orientations of p--o6itals. only, those oI multielecttun atoms dependbolh upon
principal quantum number (n) as well as azimuthal
Thus unlike s-orbitals, p-orbitals have direc- quantum numbet (l).
tional characteristics and hence are helpful in
predicting the shapes of molecules. Further it may
be mentioned that every energy level with,l greater
than t has three p-orbitals. As a increases, these
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3144 N e ut Co urse Ch c m i strgYYTl
4s 4P 4t
o
3s 3p 3d
(,
4s -9
E *
oz
E.
2s 29 OE
#
1s
1s
Some important observations from energy The order in which the energies of the orbitals
level diagram of multielectron atoms maybe made increase and hence the order in which the orbitals
as follows : are filled is as follows :
(i) The subshells of a particular shell do not b ,% ,2p,* ,3p,4s ,M,41t,5s,
have equal energies e.g. ?-s atd2p have different
. M ,5p ,6s ,4{,il, @ ,7s ,5f ,U ,'7p.....
energres.
This order may be remembered by using the
R
(ii) In a particular shell, subshell with lower
method given in Fig. 3.31. Starting from the top,
EE
value of I has lower energy. Thus in the second shell
:
N (l :0) has lower energythan2p (/ 1). Similarly the direction of the arrows gives the order of filling
AR
4s<4p<4d<4f.
S
N
Lower tlu vahrc oJ @+l) lot qr. orbital thc lower sane (t + l) vdttc, the orbital with lower vabu o!
i; ils erargt Hence orbitah are Jilld in order oJ n has hver uurg and hcnu itfrlldJint.
increasing (n+l) yalues. If mo orbitab have thz The followingtable illustrates the (a + /) rule:
If an orbital is represented by a circle aad it Since there are three p, five d and seven f
contains two electrons, it is represented as R
orbitals, therefore the pairing ofelectrons will start
EE
in the p, d and f orbitals with the entry of 4rh, 6th
i.e. the two arrows must point in the opposite direc- repel each other. Hence they spread out and oc-
N
tion. The electrons are said to bo paired or the cupy the identical orbitals singly before they begin
IA
orbital is said to be fully hlled. It will be wrong to to pair. As a result, the repulsions are minimuLm.
IIT
oor o
and is said to be half-filled. Tbe electron is said to
because of the fact that such a state has lower
energy a.nd hence is more stable.
ls Zr fp ls
Hydrogen 1
Helium
Lithium 3
o o
Beryllium 4
o @
Boron 5
6
E o
C-arbon
Nitrogen 1 o @
Orygen 8 E @
@
I
Fluorine 9
Neon 10 B
E
o
Sodium 11
Magnesium 1Z @
B @ @
The above method of writing thc electronic Chromium (Atomic numbcr = 24) :
R
EE
configurations is quite cumbersome, Hencc, usual- Expected configuration :
NUMBER OF
1:2 %2 2p6 3p6 f 4s1
S
29):
N
other in order of increasing energics of the orbitals, 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d5 5sr
starting alwals with thc orbital of lowest cnerryi.e. 1s. Palladium (Atomic number = 46)
Using the above method of representation,
- Expectedconhguration:
the electronic configurations of the various ele-
ments are listed in Table 3.4 on page 3148 to3149. h2 b2 2p6 k2 3p6 3d1o 4s2 4P6 4dB 5sz
The reason for the tendency of the subshells to be completely filled or exactly half-filled is that it
lcads to grrat€r stability.
Cause qfgluter stdbillty of exactly half-lllled and completely lllled contlguradons. The greater
stabiFty of these configurations is due to the following two reasons :
(i) Syrnmetry, The half-filled and completely filled configurations are more symmetrical and syrn-
metry leads t.t gteater 'r,hilify
(ii) Exchang€ encrg/. The electrons prcsent inthedifferent orbitals ofthe same subshell can exchange
thei e results in release of energy, called exchange enerry and hence leads
to a
' aha r of exchanges that can tale place is maximum in the exactly half-frlled
ts (i.e. more in I than in / and more in dlo than in /j, therefore
exchange energr is maximum and hence the stability is maximum.
The number of exchanges that can take place in / configuration are as follows :
-
l
,K\
[rll] rL ]
3 EXCHANGES BY 2 EXCHANGES BY , l EXCHANGE BY
ELECTRON 1 ELECTRON 2 - ELECTRON 3
Ibtal number of exchanges = 3+2+ 7=6
The number of exchanges that can ta-ke place in d configuration are as follows : -
R
<SI 3 I
EE
AR
t t 1 1 1 t t t t t I I I t
C
ELECTRON I
N
Some lmportant polnts in writiEg For elements with very high atomic numbers,
electronic conliguratlons. While writing the some deviations are observed other than on ac-
electronic configurations, the following points count of half-fi.[ed and fully filled subshells. How-
may also be noted: ever, for our purposes, such exceptioos are not
(i)To avoid the writing of electronic con- importart.
figurations in a lengthy way, usually the symbols Uti I ityllmportatrce of studlng electronic
[He]2 [Ne]lo, [Ar]18 etc. are used as the first part
, conliguration.In the end, a student maybe curious
of the configuration. Such a sym.bol stands for the to know as to why we study electronic confrgura-
elcctronic configuration of that inert gas and is tions. It is importart to know that according to
usually called the core of the inert gas. modern approac\ the chemical behaviour of all
(ri) Although the orbitals of lower energy are elements and compouads is explained on the basis
filled Erst but the electronic configuration ae writ- of their electronic configuration e.& why atoms
ten not in the order in which the orbitals were hlled combine to form molecules, whysomeelements are
but in the order of principal quantum numbirs. metals whereas others are non-metals or why some
(rr) Unless otherwisc meutioned, electronic elements Iike alkali metals and halogens are highly
reactive whereas noble gases like helium, neon,
configuration always meam the electronic con-
argon etc. are not etc.
hguration in the ground state.
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314A
14 si 1Ne1lo :s2
1Ne11o ss2 rf
. .46 Pd [IG]s ldlo 5ro
C
15 P
AS 4d1o 5rl
S
17 1Ne11o
In [Kr]36 4d1o 5s2 5p1
IIT
AI 3P5 49
18 1l.te]lo:s2
or ts2 ,Nz ,zp6 ,Nz ,zf 50 Sn lrc)ts tn
*ro tt'
19 K [At]l8 4r1 51 sb [Kr]:cttot'"
20 Ca [Ar]18 4.r2
52 Ib Il{il$ Mlo 5s2 5P4
[arlla rr' *'
2l 53 I Uklx 4dto 5s2 5P5
II tArIs 3d2 4rz 54 Xe lKite *'o tt" to'
23 lerlte ,' *'
ot ts} ,2?2p6 ,k2 3p6 M1o,
rt *t 4s2 4p6 Mro ,ssz 5f
\Xz4 Cr larlts
25 Mn [Ar]18 3a5 +rz
55 Cs lxels4 tur
56 Ba 1xe1sa rs2
26 Fe [tu]18 31 4s2
n Co lArlte ar' *' .57 la 1xe15a sa1 er2
E
ed8 4r2
.58 Ce lxel54 4/ 5d1 tu2
28 Ni lArf
\-b1e Cu [arlte *t 59 Pr 1xe15a lf s/ es2
Ztt
'O''o
,to *' @ Nd f/'fil'4 4f 6s2
30 [Ar1ts
31 Ga lr'jl1l M1o *2 4P1 61 Pm 1xe15a tf *7
*' on 62 Sm lxels4 4f 612
32 Ge l*fe :,oto
-.Elements
with elerlroDic confisuratioDs.
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ATOIVIC STRUCTURE
(Unnithexium)
80 Hg lXelsa tfa 54ro 6z 107
C
or Bohrium
N
fi%
I 13 Uuo [Rn1% sla ulo l5z 7oz
U lRnls 5P 6dr tu2 lUnunqua'diuml
t|93 Np 5f dt ll4 Uuo
[Rn)% 7s2 lRnlu 5f4 6d1o 7s2 FF
(Ununpeh um)
94 Pu lRnls sf tuz
O,N ELECTRONIC
l l i:;ii ,, ....,,,, .,,,,,
CONFIGURATION
(atomic No' 15) chromium
i I . \ '. r 1 . l.Find.lhe number ofurtPoircd electtons Prcsent in Phosphorus
(atomic No. and coPW (atomic No'29) alter witing theit orbital electmnic configtration'
Solution.
At. No. Etectronlc conliguratlon No. of unpaired electrons
Element
P 15 t* ,xz zp6 ,x2 yt,qtrlpt, 3
atonric numbers :
li', | .l.Wite the elec7onic configurations of the elements wilh the following
3, 8, 10, 14, 17, 25, 29' and 3E'
belong'
Also mention the gouPs of the peiod'ic table to which they
Solution.
Atomic No. Electronlc con[iguration Group ot pertodic T[ble
r,"N1 1
,5
8 t"'x'Ulzp)zpt, t6
10 t"'x'zplzptrU1 R 18
EE
14 ti xz zp6 xz lp1,lp1, t4
AR
lsz k2 3p11ptr3p1, r7
t7 zsz ?p6
C
25 1s2
N
38
l:'. I I I'l
29 electrons an
of protons and
element.
(i) Scandium (At. No.21), aod (iiD b2 xz 2p6 3sz 3p6 3d5
(ii) Chrcmium ( (iv) tsz ?s2 2p61s2 3P6 3t 4s2
t '41 1,t"-, G z? tp! zp!, tp! #
1i7
4"lI
2. Write the electronic configorations and the names
1ii1I;*at.zp!,wl
of ths elemeDts having theatomic numbers 5,9, 10' @ir;:4,zp632b5&#
Q") G 2i 2?6 3? 3P6 # *tl
19 and 20.
,r;s = i? z's? 4e s? h6
N
M6.
S
N
IA
IIT
o_n-a*_a_PI
of the gas tEide the.discTTj:.:-:-::."'::
Q. Why cathode rsys are produced onlywheE the Pres6ure
l.
current lloqa through the tubc bcause gases
Lo e, iiglr", pr"oure (e.& at 1 atmosPheric pressure)' no eleatric
are Poor conductor of electricity'
q 2. Give two examples from evcryday life rYher€ cathode ray tubes are used_
tub€s'
Ans. (i) Teleilsion picture tube (ri) fluoresceflt light
rays altd anode rays ?
Q l. What is the ililference in the origin ofcathodc
aDode rays are Dot prod"red from the anode They
arc
uhereas
**
Ans. Cathode rays originate from thqcathode
by hiSh speed cathode rals'
pt.ii"*oii", th"e gaseous atoms b'y knock out of tI e electroos
gas is taken ond in the other 02 gas is taken' will the
electrons and positive ions
Q. {. In one discharye tube.II2
diffcreDt ?
in the cathode rsys srd in thc anode rals be same or
same'
Ars. Electrons will be same but positive ions will not bo
foil of gold, very few a-particles are dellected bacL lvhat does
it prove ?
Q. 5. When a-rsys hit a thin
within the atom' called nucleus
Ans. There is a very small hea\y body present
atomic mass and ltrs'ss number ?
Q. 6. What is the differelrc! between
it the sum ofnumber oJ Protons and number ofncutrons whereas
Ans. Mass number is a whole number because is
aton]
mass of iis atoms as comPared with mass an
atomic mass is fractioout o"""rr" it i. tt average relative
"
of C isotoPe takeo as 12'
- 12exaEple
Q. 7 Give on. of each of the following :
(i) Isotopc of i;cl (ii) Isobar of flAr R
(iii) Isotone of |ac
EE
14 A60
(ii) A triva
IA
'quanta'
photon ?
Q l l what is the differ€nce betweeD a quantuE alld a
photon'
is allcd a quantum whereas that oflight'is called
Ans. The smallest packet of energy of any radiation
cach other ?
Q ll. Ilot sre flequency ond wave number related to
=21 8 x10-19J.
r.) -ll R
What is the maximum number of lines obtaioed when the excited electron of a H atom in,l = 6 drops to the
EE
ground statc ? (N.C.E.R.T.)
AR
tu$No.of a (a-:11 1)
lines produccd when electron fiom n th shelldrops to ground state - -6(6- -r,
C
Ans. In the presence of magnetic field, the orbitals present in a sub-shell (which were degenerate) take up different
C
orientations.
(.) 1l How many electrons in sulphur (Z = 16)canhaYcz + r= 3?
S
N
Ars. = 1122?2P53s23P4
IA
16s
IIT
Ans. This is because acmrding to this principle, if one electroD in an atom has some particular values for the four
quantum numb€rs, then all the other electrons in that atom are excluded from baving the same set ofvalues.
{.) tl Horr mary orbitals are presetrt in the M.shell ?
turs. shell (r) Sub-shells (0 orbitals (m)
3 0(3s) 0 = 1
1(3P) -1,0, +1 = 3
2(3 d) --:2'-1'O' +t' +2 = 5
Total = 9
Altcrnativetlt no. oforbitals = n2 = 32 = 9.
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ATOI\iIIC STRUCTURE 3157
Q. 9. Write the expression for the energ5r ofelectror ofhydrogetr atom in tbe rrth level.
4,,". 5- =
-lLl2umsl-r.
n'
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ltradet,lt's Neut Coursc Chemistrrf lfim
3/58
Ans. J-orbital.
Q. 12. Which quallttlm number deterEines the
(a) shapc (r) oricntation and (c) size ofthe orbital ?
Ans. (a) Azimuthal (D) magnetic (c) PriociPal
Q. 13. Which cnergy leycl does not hove ap'orbital ?
How can you say that electron is a universal constituent ofall atoms ?
3. Givc expenments to show that
(i) Cathode ra,s carry Degative chargc (ii) Cathode rq's consist of matcrial particles'
Scc.3J. 4. How was proton discovered ?
Scc.3.4. 5. What was Thomson modelofatom ?
to 3.5.
6. How can you say that nucleus is small in size but healy in mass ?
to 3.10.
Scc.3.11. 11. What is Planck's QuaDtum Theory ?
Sec.3.12. t2. Hop is the aromic sperra of hldrogen obtained ? what are the differeDt series of lines pres€nt in it ? In
which regions do they lie ?
13. what is Rydberg formula ? How does it help to calculate the wave numbers ofdifferent serles oflines
of the hydrogen sP€ctra ?
14. what is the difference between Rydberg formula and Balmer formula ?
Scc.3.l3. 15. What was the drawback of Rutherford's model ofatom ?
Sec3.14. 16. What do you understand by statlonary states ?
to 3,15.
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AIOI\,4IC STRUCTURE 3159
77. Whar do you mean by quantisation of electronic enerry aDd angular momentum ?
It. Holx do€s Bohr model explain the linc spectrum of hydrogen ?
19. Hcw do€s BohI model explain the simultaneousappe8ranc€ ofa large number oflines io the hydrogen
spectrum ?
20. Outlioe the w€€lness€s of Bofu's model of atom.
Sec,.l.l6. 2t. What happcDcd to Bohis model of atom in the light of uncertainty principle ? Explain rhe coDc€pt
of 'probability'. Define 'atomic orbital'.
scc.3.t7. Ho are the quantum Dumbers related to each other ?
S cc. .l.l li. 23. DeEne Pauli crclusion pri[ciple. Why is it called exclusion principle ?
Scc.3.l9. 24. How do b, 2J and 3s-orbitals differ from each othcr ?
Scc.3.20. State and €xplaiD 'aufbau principle.'
to 3.l, t.
26, State and explain'HuDd's rule of maximum multiplicity'.
'Why
do some atoms pcsess €xccprional electronic configuration ? Fl(Plain with suitable ammples.
z. How are cathode rays produced ? Briefly explain their important propcrties.
I What are Anode Rays ? How do they originate ? Ljst thcir important propcrties.
4. Briefly d€scribe Rutberford's scatEring experimeDt about the discovery ofnucleus.
R
EE
5. Hc,u, was tbe nucle€r model of atom discovered ?
6. Ho|l was neuuon discovcred ? Describe briefiy.
AR
7. (4) Define the terms Aromic Number and Mass Number. (6) Holv dcs mass numbcr diffcr ftom
atomic mass? Ho\x do atomic number (Z) aDd mass oumber (A) help to calclllate the Dumber of
C
E. What were the main poiDts of Electrc'nagnetic wave theory ? Wbst v/ere its limitations ? How have
N
Bricfiy explain what do rou undersEnd by black body radiation and photo€lecrric effcct ? What is
IIT
work function ? How they led to the concept of panicle nature of electromagnetic wa\rcs ?
10. lrty'rite siort notes on thc followiDg :
I,OiNAl;U,s.E
l.canwescethcotoms?ForthelastDearty200years,theatomswerebelievedtoqistbuttherewasno
strow ttleir existence. It is only rec€ntly that the-direct photographs of the atoms have
been taken
oirectlrooito
using i tcchnique called ScanEing Tlttrreling Micrmcopy (STM)'
in 1895 observed that when cathode rays hit the anode
R
EE
AR
C
S
N
IA
IIT
3'BohrBurySchemeofdistributionofelcctrons.Todescribclhedistributio[ofelectronsindifferent
orbits around the nucleus, Bohr and Bury in 1926 put forward the follo\ irlg scheme :
(i) The maximum number of electrons in the,th orbit is givcn by the formula 2r2
(ii) The outermost orbit cannot have more thao 8 electrons and next to the outermost not more than 18
electrons-
(iii)Itisnotoecessaryforanorbittobecompletebeforcanotherstaltstobeformed.Infact,anewolbit
starb as sooo as the outermost orbit has got 8 electrons'
4. Calculation of radius of the orbil In a H-hke particle, for the electroo to coniiDue to move aloDg the
orbit of radiust,
electron
Force ofattraction on the electrcn by the nucleus = Ccntripetal force acting on the
:!/60
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ATOMIC STRUCTURE 3/61
where ,?l is
==.+
f'
the mass and e is the charge on thc
electron, Z b atomic no. of the HJike particle (a& for
,Je+ ,z=2, for u2+ , Z=3 etc.) aDd u is the tangeDrial
wlocity. Also acmrding to Bohr's pctulale of angular
momeDtum.
mrr=n* h *(ii)
EliminatiDg u ftom eqos. (i) and (n) (by su bstitu ting
value ofr, ftom (ii) in (i) aod rearraDgiog), \xe get
n2 hz Bohr's Fltke atom.
...(rir)
4* m ZnL
For H-otoE, Z=I and fot lst orbit, n =I so that
Thus
o
For HJlke otomq ,o =
tt L
rn(,l-al,m) R
- o szg n2
EE
and rr(H-tike atom) -
^
AR
t t ( 2.2\
S
=_n"-+\_ r )
N
IA
- 722
zf
722
f
7"2
,tf
Substituting thc value ofr ftom eqn. (ii), we ger
2.2 4r2m7z2 2 rz mz2 e4
-L= -2-x--An-= ----1"-
NotcthatKE. =4,r.r.= -4,-n,r^,"n rg.(\d= -+
... Erot.t,/KE. = (- Zz2 /2t),/ (7zz /2r) = - 1
ADDITIoNA_L-ueE-f qLlNEoR.!Y!AT!9!.1-c_ol1td
On substituting the values of the constants n,e and h,we get
108 cm s-l
2-lfs x ro8"rnr-1
o^=f; xx2.l8S, I
Fhrther puttint n = 1, the velocity of electron in the first orbit of H-atom will be =2 lt8 x lotcmr-1
which is nesrly 1/137th of the veloclty of li8ht.
-7
AIso, from eqo. (i), it may be seen that ,2 =24 *61slr tho*s,l'tr, ""+
?, Cslculation of the number of rcvolutions of the electron in an orbit per sec
hnh ,;
By Bohr postu late. n ur = n i7 or = 1;;;
Number of revolutions per sec = -f49SU-9!!9-9'iss!!9!-
R
EE
2ttt
AR
2ltlrlf ,f=
= l< fon substituting the value ofu)
=4! lJtf
C
-. (ir)
S
1 it' nf
N
4t?n?
IA
-.2
No. of revoluiions rer sec 'f
=4n'm * i
lo {.?'\
' ,'h'
\ )
+,?m7]ea
nJ hJ
Er
= --F 11\
l7)
where E1 = -'"'Y"n rrrr"eners/ of the tirst shell.
2nrmo -tr-
- ---i- - 2 (tn
. u o"
2 nh -
- -i-
z; n
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ATOIVIC STBUCTURE 3/63
nns. E,
" 1... s " ]r". + " *,+ " ) Thus, the ciromferenc8 (2 zr) ofrhe Bohr orbit
for hydrogen atom is an integral mulriple of dc
C
Le-
l_
E2eT I BroSlie waveleogth.
\(r7,
S
a.
IA
For He+ rco,Z = 2and for the first excited state, ADs" they had parallel spins, tbe repulsion will in-
If
n crease. As a result, enerry will increase and the
=2 stability will decrease.
^2
%:-R,i=-R" Q. II. The eleEeDts P (Aton c ldcight 39) aDd Q
(Atomic $'eight tO) contalu 20 ard 45 oeutrotrs
Ilence the required result is pror'ed. respectively iD their Ducleus. Glve thclr
Q 7 @) Derive the relationship betwecn the electronlc arraDseDcnts Eeparat ly
waveletrgth associated with a moving Psrticle (I.S.M. Dhortud 1991)
ond its kinetic energs[ For elemeDt R A = 39,n =2O. As A =P + n,
^=*\/#-#
C
h=4
or nz =lf :e or n=3 rrusrx"=f =n,
[+-+, =",
C
= (0
IA
Rudir. ,' =
h' l't ol.h Di lt) Celculste the radius of Boht's lifth
12 . orbit for hydrogell atom, (N.C.E.R.T\
4*mZe'
For H-atom, /,, = o 529 x n2 A
t2 x (6 63 x 1o-27 erg sec)2
- R
*ff)',<s :.rs=O 52:9 x52 = 13. 4 = 1.3225!lm.
EE
11x10-28g; x (4 8 x 1o-roesu)2
I'rohlu ll. Thc aDgular mometrtum of atr
AR
/',.,r,,1, CElculate the enerB/ requir€d for th. 4.22 x 1lo-v kgni s-l' catcul.t the wavelctrSth of
S
Processi thc spectrrl linc t?h.n thc GlcctroD fslls ftom thls lcYcl
N
Applyiog Rydberg's formuta firsr ro case (r'i), wc ger Ionizarion potenrial ofH = 13.6 ?V meaDs thar
l?-6"v,
v=l=nz'11-11 = - 13 6eV,B = -
Er,"21
^ l* "i) g' = - 13.3"v
'3.
R
Energy released ftom all aioms when electrons
EE
return from 3rd level to 1st level
AR
-1-0.75=025 / 136- tt \
= o) x zcz 68 x ro2rev
S
ot "1
ni=Oi=4 ot nt=2 [- i=
N
3 x
IA
By mole conc€pt, I g of hydrogen atoms For Be3+ 12 = 4), ifzth orbit has rhe same radius,
conta x loa atoms
_.
then
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3/68
I'rohlon T The ionizrtion energt of hydmgen
o 52gx+=o 52sornz = 4ie D=z atom is 13 6 eV What wtll be the ionization encrE/ of
He+ and Li2* ions ? (Roortce 1986)
+
Thus, second orbit of Be3 ion has same radius as
tbat of ground state (1st orbit) of H-atom' ^ 2r2 m 7]ea for hydrogen like
I'ril'lu l Nt elcctton iD a certain Bohr orbit has n2h2
particles
velocity U275 ofthc velo.ityofliShl In which orbit the
Glectron is revolving ? LE,=E--Er
Velociry of electroo
^ ( 2n2
='-[- ^zz
ea \ -L,1mzz ea
=fi"z"1olocms-l I )-----T
= 1 09 x 1oocms ' Fot H, z= 1 tz = 4!! = n a.u
VelNity of electron in nth orbit of Hlike particles ...(Given)
in C-G.S. units is given bY
For He+ ,2 = 2,1.E. = 13 6x7?
2nZz2
!r-_T =136x22=544eV
PrrltiD.gz = l for H and e = 4 80 x l0-l0eru (in For L?+ ,z=3,1.8 = 13 6 x 32 = l2z 4ev
C.c.S. units) andll = 6 626 x 10-27 erg sec, we get I'nthtut 8. Calculatc the velo.ity (crn/sec) of an
clectron placcd in the third orbitofhydrogenatom' Also
- z ts n to8
2 x.1 14 x (4 80 x l0-151 x
colculate the number ofrevolutions Per s€cond that this
,r x (o 626 x 10-27) electron Eakes around the [uclerts. (knrkee 1987)
2 18f< 108 R As derived on Page 3/61
- 1'09 x 108 (calculated above)
EE
24 z.ez 2x3.14x 1x14 8x 1o-ro;2
' n=2 "=--nE-= \6A;1o=--
AR
3
l\,,|'lut ; S laser emils moDochromatic radia-
=7 27 xl cm/sec
C
Pe
IA
( nzhz \
'"lnl^a1
4*mtzez 2t mo zex
= 3 x lo-19 J 2, na hz n2 h2
2t .7g x to-tg
= 13.6eV (.. IeV = I.6 x 1o-leJ)
x 22 -
= - _-_-_ =-9.68x10-19J
I'rohlun 10. (a) Electromagoetic radiation of 3'-,
wavelength 242 Em is just sumcietrt to ionize the Enerry required to remo\,re the electron
sodium atom. Calculate the ionization energy of sod iuEt
in kJ mol-I. = 9.68 x 10-le J
0!1678
=0 494 x to6 J mol-l = 494 kJ mol-l
C
)
LE. of H-like particle =I.E.of H xt
N
, lr 1\
IA
Solution. =R
=ExZz l?- 4)
IIT
^E=hv=hI
tr l=0ju
= 3 0346 x ro-19 J/g atom
. 11,.14 x l|-rs z7 = 6 62b x to-'o
' =3x 10-6 to-le; x 16 02 x l0a)
3 = (3.046 x J/atom
R
= 18 268 x ld
EE
6 626 x 10-18 I o6o12=2. J/g atom
or z2 =i;?;; t+$ =
AR
I't,:i'tttn IJ What transition itr th€ hydrogen by a Bohr electron in its 3rd orbil (I.I-T. 1994)
S
Solutio_E For Balmer series,41 = 2_ Henc* wavelength ofIIe+ ion. <I.I.T. 200j)
C
\22 nl )
'=r="ft-i)"'
N
IA
, = i. t
IIT
1. The charge on the electron was found by 9. The ratio ofcDers/ of photon of,t = 2O0oAtothat
of I = /|om A is
(4) JJ. Thomson (6) Millikan
(c) hraday (d) Goldstein. .@\2 (b) r/4
\t t.t. tu\..
(a) JJ. Thomson (b) Chadwick
10. Anyp-orbital can ac{ommodate upto
(c) Rutherford (d) Moseley.
(a) four electrons
3. WheD.r-rays slrike a thh foil of gold (b) two eiectrons with parallel spin
(a) Most ofthe a-rays are deflected back
(b) All the @-rays Pass through the foil -{d6(clectrons
clectrons with anti-parallel spin.
(c) Most of the d-rays are deflected through cm3!l /Urytwo ,r t. r: r,t\tt
angle
11. lluthcrford'sscattering experiment is related to the
(d) Most of the a-rals pass thrcugh without any
deflection. E the
size
(c) Paschen
(one or more)
Pascben series are Producrd \rhen electrons from (4) a-particles are much heavier than electrons
C
(b) a-par
(a) 2od orbit (6) 3rd orbit
N
6. is
a r&d a
/<s
76.
26. c
17. b
27. b
19. 2O. o 2tb 2Lc 2t. b Z4.d ZS. a
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3n4
35. The orbital aDgular momeDtum of an electroD in
(c)n=3,1=t,n=-Z,s=-l 2 r orbital is
th
(l)n=3,1=O,m =0,s= +i
1
(4) En€rry of the elecron in the orbit is quanl ized (c) cN- (d) oz+
(D) Ttle elecron in the orbit Dearst to the oucleus (. I!,1!.1: l r97
C
t R.S. 1,.
has tbe lotPer energY
S
(c) An8ular momeotum ofthc electron in the orbit 40. The Bohr orbit radius for the H----atom (r = 1) is
N
is quantis€d
(d) The position and velocity of the electrons in the excited state (z = 2) orbit is (in A).
IIT
A
2E. a,c 29. c 3(Ld 31. l, 33., 34. c 35.b 36 a 37. c
3A. b X9. c 4o,4 .-* 4t- a
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ATOI\4IC STRUCTURE 3ns
(4) Tbe electronic coofiguration of Cr is 51. Among the following groupings which reprcscnb
lr'trl t1 (Ar. no. of cr = z)
3 ds 4 the collectioD of isoelectronic speciqs ?
(6) The magne$c quantum numb€r may have a (a) No+, q-, o2-, co
negative\lalue.
(c) ID sih/er alom,23 elcctroB hatr€ spin of ooe type (6) Nr, q-, co, No
aDd 24 of the opposite type (Al. no. ofAg = 47)
(c) co, No+, cN-, cr-
(d)'Ihe oxidation state of nitrogen in NHI is
-3.
( l.I.'t: t993.| (d) NO, CN-, N2, O;. i ti \ . tlt.t t ;,ti)t ,
44, The enerry of an eleclron in the fiIst Bohr orbit of Tbe energy of a photon is given as
H atom is .
6 eV The possible enersl l?lue (s)
-13
of the € ciled state(s) for electrotr in Bohr orbits of AElatom = 3.03 x 10-19 J atom-1. TheD th€
lrydrogen is(are) wavelength (t) of the photon is
(a)-3.4eV (b) -a zev (a) 65.6 nm (b) 656run
(c)-6.8eV (d) + 6.8eV tlr.'r. teest (c) 0.656 nm (d) 6.s6wn.
45. Who modilied Bohr's theory by introducing ellipti- t ( . It. \. L. L,t L'l: 20t)t) t
47. Magnetic quantum number specifies (c) He2 + (d,) H. D. L. 11. i:. l'. : tt ()t )
)
S
(c) (0 < (,,,) < (rr) < (iv) 57. Which of rhe follotying atom has Do neutron in its
Ducleus ?
(d) (,rl) < (r) < (tv) < (rr) (I.I.T r 999)
(a) Helium (6) Uthium
49. The number of nodal planes iD apr orbiral is
(c) Protium (d) 'Ititium.
(a) ore (r) two
\< .f ii!.'l )t)00\
(c) three zero. t i.l T 20A0i
(d)
The electronic configuration of an element is Ifthe radiusofEIst Bohr orbit be 40, then the radius
l s2 2s2 zf 3 s2 3p6 3 d5 4 11. This represents irs ofthe third orbit would be
(a) excited state (r) Sround state (b)6xao
(c) c€tionic form (d) anionic form. (d) 1/9 x ao.
!l.l. t: 2t1001
:
43. a,b,c 44. a 45. d 4.d 47.c 48. o 49.a 5(I, 51.e SLb
53. rt 54. c 55.c *..1 S1.c 5t. .
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3176 Pradeep's
In Cu (Ar. No- 29) (a) Mn2+ (D) Fe2+
(a) 13 electrons have spin in one direction and i6 (") Ti'* @) cc+
electrons in other direction ('1 I l' L lt 20(t)
(6) 14 electrons havc sllin on, dircction ard 15 67. Which of thc following element outermost orbit's
electroDs in othel directio[ last elcctroD has magnetic quantum Dumber rn =0 ?
(c) one electron can have spin only in the clockwise (a) Na (D) o
directioD
(c) cl (d) N
(d) none ofthe above is correcl.
(Rqastlwt PM T 2002i
\HaDa rt L E II l:2t)0t)t
6& In hdrogeD atom, enerEr of the first exciEd state
The following quaotum Dumb€rs are possible for is 3.4 e\l Th€n find out the ICE. of the same
how maoy orbiials ? n = 3,1= 2,m = +2
-
orbit of H-atom
(a) | (b) 2 (a) + -? 4eV (6)+68eV
(c) 3 (d) 4 (c) 13.6 eV (d) + 13.6 eV
t( .lt..\ l;. l!,ll.l: )01)l t
- (c.ll.s. D. l:ll'l: 2002 )
| I
il
N
(a) increase (b) increase very rapidly lf the Nitrog€D atom bad ele,ctronic coo.figuration
IIT
(c) increase very slo tY lr?, it would ba1,e cner8y louer than that of the
(d) fall normal ground state configura on ts2 Nz zf ,oe'
(d) enerry remains constant caus€ the electrons would be clocer to the nucleus.
( kroln tll l: l; )()lD l Yet 1s7 is not observed because it violates
Chloride ion and potassium ion are iso€lectronic. (a) HeiseDbers's unc€ ainty PrinciPle
The. (6) Hund's rule
(c) Pauli exclusion princiPle
(d) their sizes are same (d) Bohr pctulate of sbtlmaryorbits (1 1.7: 2002)
(b) chloride ion is bigger lhan potassium ion 72. In Bobr series of lines of hydrogcn spectrum, tbe
(c) potassium ion is relatively bigg€r third line from the red end corresPoDds lo which
(d) depends upon the othcr cation or anion one of the following inter-orbit jumps of the
\ tr: ( l:"1: )t)tt) electron for Bohr orbits in an atom of hydroBen ?
oQected to be similar to that of
'
(a) s- 2 (b) 4- 1
The spectrum of He is
(t) Na
(c) 2- s (d) 13.- 2
(a) H (A IL I'' Ii )0011
(c) He+ @)u+ 73. The number of d-electrons retaiDed in Fe2+ 1At.
(lr.P. PM.T. 2002 No. of Fe = 26) ion is
Which of the follo ing ions has the maximum mag' (a) 4 (D) s
oetic moment ?
W
77. The ftequency of thc radiation emitted wheo the
(d)9 (A.I.I.M.S. 2oo4) (a) H (E) He+ (.) Ba+ ((rLiz+
(Kadla C.D.D. 2004\
efectron falls ftom n = 4aon = l iD a hydrogen @)B*+
atom will be (Given ionizatioo enerry of H 66; nme laken for an eleclroD to complete one tevolu -
tioD in the Bohr orbit of hydrogen alom is
- 2.lt x I -18 J atom-l aod
h - 6.68 x 1o-r Js)
O
o+
R @)#,* @##
EE
'!?f3'c8 x (rkrot.prv..t:zoott
rcts t-r (d)2Oxlorss-1 t7" If ltle ionizatioo encrsr of hydrogeo atom is 13.6
C
7& The radius of which of the follot ing orbir is same state to the next higher state is nearly
N
IA
,E
73. c 75. c 76. c 74. d 19. b E0. c 81, tl AL d
E3. E5. 15. a EE. d r9., 90. c
' '
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3178
Ne@ Course chemistrgWA
Rather enerry t'ill be releas€d' 43, 'fhe oddation stale of N in NH3 is +3.
N
44, 11!,',r
4i2 n7'"
IIT
65. I Ic has two ele.ctrons. Li+ also ha.s h+o electtons. aE = Ft- F, - - 2.1e lo,t il-*l
C
=2 044 x to-18Jatom-1
N
=3085x1015s-1
24cr = [Ar]t8 3d5 4r1 .- cr2+ = ttuf 3#
8
n. r^-L ..!D-!z-tr
Thus Mn2+ has maximum number of u[paired
clcctrons. . rrlni =9L\x f = o.s2eA
67. I I Na = tsz 2s2 2p6 Zsl i.e. tor last electron I = 0
.. rz =0, rr1Bc3+1=9iPJ!= o 52e A.
6& llnergy in rhc excited state h nothing bur KE. 79. TnCr = 1:t2 zJz 2p6 3s2 3p6 3ds 4s1
69. v.B. =)r^o2,r.8. = -+ I= 1 meansp-sub6hell and, 2meansd-subshell
=
I- 1 is fot 2p6 aftd 3p6 -.'Ibral eleclrons
= 12
But eleqrostaric force ,$t = d Gcntrifugal torel I= 2 is for 3d5 . .. 'Iblal clecrroos
= 5
speqes-
, = 3, 1 = 0 mcans last shell is 3r
'. E.C. will bc ,tz vz 2p6 Nr-2.
..13 67] = 54 4or7] =4orZ--2ie.He+ Atomic no. is 11 or 12.
hnh llumbcr of
t6. By Bohr Postulate, mu, = " f;ot " = ,h 89. lsotoncs arc atoms conlaining the same
neutrons (No. of n = A - Z). No. of nculrons in
No. of r€vdutions Per sec
!!ce = x - zz = lt. !f;se has Deutrons
- Circumfelence of thc orbit
=7a-34-44.
rnhlnh
E.C. of 28Ni - B2 2s2 2p6 kz 3p6 1d8 4s2
ADDIT'ONAL 8$ESTTONS
As s erti o n-tr-e a e o n TY P e Q.u e eai on e R
EE
Thc foltowlng qucstloDs cotraist ol two st temetrls eech printEd as Assertion and Reason. lvhile ansrrering
thcs. qu€stioEq you src r€qulrcd to choose any ore of the follo! ing llve responses'
AR
(a) rboth Ass€tioD aDd Rcsao! or. true and the RGssoE 16 o corTect explanstion olttre AssertioD,
C
(D) If both Assentol and Rcrsotr ar€ truc but Rcason is not a corr.ct exPlaDatloD of tbc Ass€rtioD.
S
(c) IfAssertion 18 truc but the Resson is false. (d) If the Assertion is false but the Reason ls true.
N
IA
Ass€rtion Reason
l. An orbital cannot have more than two electrons. Two electrons in an orbitalcreate opPosite magnetic field.
The configuration ofBe atom cannot be 1t2 3 12. Hund's rule demaDds that the mnfiSuration should dis-
play maximum muhiPlicity.
1 p-orbrtal is dumb-bell shaPed. Electrons present in P-orbital can bave any one of the
three values of magnetic quaotum number t. e. + 1,0,
-l
4. Wave number of a spectral line for an electronic It is proportional to the velocity ofthe elcctron underSoiog
transition is quantised. the transition.
5, A spectral line will be scen forazpr - 2Py fiansi- Energy is released in the form of waves of light when the
eleclron drops lrom 2 /rllo2pyotbital
tioD.
U.I.I.M.S. 1996')
re are many ocited enerry levels aYailable.
(A.IJ.M.S. 199D
Tr u e / tr a Is e gt at e m nte p-
wich of the lo oteing sla,n,nrs ae true ? t.
Rutberford's model catr €rplain the line specrum
1. No current flou{ through the discharge tub€ wben of hdrogen.
the pressu re of the gas iDside is one atmosphere. 9. The eners/ levels are called stationary states be_
The cherge on the parlicles coostituting the anode cause the ele€1rons are stationary io these leveis.
rays does not depend uFrn tbe nature of the gas 10. The energies of different shells are in the order
takeD.
K>L>M>N......
3. Arode ra,s originate from the anode.
11. Eledmnic eDerEr is netati\€ becaus€ electron bas
4, The magDitude of charge on an electron ard a negatiit charge.
proton is the same.
12. Bohr's model is not in accordaDce with de Broglie
The mass of proton is nearly same as that of concept and Heis€nberg,s uncertainity priDciple.
hydrogen atom.
13. Tbe bouDdary of an atomic orbital canDot be
All elecromagnetic wavEs travel witb the velocity defined with abEolute accuracy.
oflight.
14, All orbitals have directional characteristics.
7. There is no diffcreDc€ between line spedrum and
atomlc spectrum.
2. Carhode rara produce.......on s[iking a ZnS screeD. 17. The energr of a 4r orbital is....._than that of 3d
3. Anode R
orbital.
EE
rays are deflected towards.......plate of the
electric field. 1E. r{rbiulls have.......shape whereas p{rbitals have
AR
.....shape.
4, Proton was discovered by.......... . h.E the
C
11. Bohr's model of atom is based upon--...-...whereas 24. The outermos! electronic configuration of Cr is
wav-e. mechanical model is based upon......... and (I.I.T. 19e4)
13. 'fhc Dumber of sub-shells iD the nrh main shell (Bihu t99n
is.........and the number oforbirals is........ . The probabitty of finding the electroD at any poinr
14. The orbitals having the same ellergr are called.... . around the nucleus is found from the v;lues
of.......--. .
15. Forz = 3, / = ......, ....., ...... .
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3182
Neu/ Course Chen istr,l Wil)
1-3,2-1,3-2,4-4.
N
IA
HlNfS/ExPLANATloNSiLoAssertion-ReagonfypeG.ueet.iono
IIT
[J hJ IT
Claeeificatto n of ElernenEs
and ?eriodiciV3r in ?ro?ertieo
,.',,',
i:
C
SECTION _ I
S
N
PEI{IODIC T.A'BLE
IA
In 1808,
Theory. Acco
element canb
basis of their
tempts on the ctassification of the elements were
b asi d up on their atomic weights'
1.. Doebereinet's Thiads. The first attempt
towards t'-f,e?Ia*itieafiOn of?fements was made by
I. DoebereinAr, a German chemist in 1817'
4t1
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412
He arrunged similar elemenlJ in groups o! three and shrwed lhtt lhs oromit ||eighlt qre eithar
nearl! the
same or tha atomic htei9fu of the midills element is (pproximalel! the urithmetic min
of the other two. ihesc
groups of three elemenls are called Doebereiner's Triadr ,
The major darwback of Doberciner's classilication was thaI the conccpt of triads coukl hc
applicd
only to the limited number of elements.
2. Iblluric R
periodic classihcation, in thc sensc in rvhich the term is
EE
now uscd, was th sa<1b'1 de Chancourtols in 1g62. The unilcrlying concept
is, however, com
AR
this book.
3.-Newlands Law of octaves,. ln 1865-66, an English ahemist, lohn Newl,andr observecl that
C
are otrafiged in,order of tlteir i creqsing atomic weights, the properties of evcry
S
N
to lhe first one like the eighth note oI (1 tnusical scale. This generalizaiion wa.s
IA
foctaves.
IIT
5r No. 1 ) 3 4 5 6 7
Elament Li Be B C N o F
Sr Na 8 9 l0 1l 12 13 l4
Elcttent Na Mg Aj si P s CI
St No- 15 16
Elzment K Ca
sodium,
Thus, to properties of the eighth element were no longer
lithium andso is the m. similar to the first one.
The same is true of al-
cium ; boron and aluminium and so on. In the
4. -Lother-Meyer arrangement. In 1869,
Lother Meyer, a German chemist, stridied the
begrnnfug this idea was not widely accepted and physical properties such as atomic volume, melting
was actually ridiculed. However, his work was point and boilhg points of various clements.
recognized much laterby the Royal Society, Lon-
don by awarding him the Davy Medal in 1887. He ph
ThLs generalization was alstr discarded since
(gon
it could not be applied to elements having atomic dlomicveiglS of E elencnts and obsumed that thc
weights greater thar that of calcium, i.e. /l{) a.m.u. ehnens wiih similsr propertizs occupid similar
Furthermore, with the discovery ofnoble gases, the posiliorx on tlu cume (Fig. 4.1).
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CLASSIFICATION OF ELEMENTS AND PERIODiCITY IN PBOPERTIES
413
E
LIJ
l
J
o
o
o
F
R
EE
AR
ATOMIC WETGHTS
C
--+
S
curves_
IA
For example,
IIT
_ lo
chemist,
1869, Dmitri Mencleleev, a
Russian Mendeleev arranged the then known ele-
used broader range of physical and cbemi_
ments.in order of their increasing atomic weights,
cal properties lo classifo lhe elemeots.
grouping together elements with similar propeities
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t)rntt a a y's Neut Coutse Chemisugl&frlD
and teaving out blank spaces wherever neces' .rty' .ulaDiuo were not
Ho also made the bold prediction that there r'ere proposed his peri
sonre uoknown elements whic[ ofcourse, wouldbe these elements as
discoverod in due course of time and would fill because he believe
thes(' l,lank spaces. Hc even predicted their alurninium and silicon resPectively. These ele-
propertiss in th; [ght ofthe properties ofthe other ments wcre discovered later and Mendeleev's
ect.
ilements in the sirme group. Later on, these uu-
as
known elements were discovered and were found
by
to possess exactly ihe same properties as predicted
by'Mcndelccv. For exa-mple, both gallium and ger-
as Predicted by
TABLE 4.1. Comparison of the properties of cka-atuminium and eka-silicorr
Mendeleev and those found experirnentally
70 '12.6
Atom:c mass 68
Q) Eight veftica
N
are designated as I,
IA
R
5B 6c 7N eF !
m
EE
6 919 9 012 12.01t
10.8',1 14.007 15.999 18.998 4
AR
3
trNo tzMg r:Al ( 0
r+Si rsP irS ncl 6
C
2299 u.3t 26.9a 28.09 10.914 32.06 35 453 =
S
1 z
N
rqK zocu zts" zzTi uc, zsM, 26Fe 17Co 2gNi !
rl
39.102 40 08 44.9(
IA 47 90 50 94 52.00 54.% 55.85 58.93 58.?1 o
IIT
-o
zlcu nZy ::A' vS" sBt m
I
63 54 us.:f, 14 92 78 96 79.9@ Im
o)
5 :rRb
85.47
:eS. :SY qoz' O'M ,rzMo ,:t *Ru .5Rh ouPd
a7.62 85 91 91 22 92 9t 95 91 (ee) 101.07 102.91 106.4
qtAg oacd aslo soS, srSb szt S:I
107.87 1't2.40 t14 82 118 69 121.75 12'7 60 126 90
6 ..Cs seBa
slLo
,zHf ltTu zw lsRe 76Os /r BPt
132.90 137.34
138 9
118 49 180 95 183 85 186.2 1 .2 t92.2 t95
lsAo aoHg gzPb s:Bi tlPo
196.97 - 200.59 arTl 201 19 208.98 (210)
2M.3',7
(discusserl in Unit 3) clcarlv ;ndicates that wirh a Consider the following examples for illtstra-
gradual incrcase in atomic number thcrc occurs a tion.
rcpctition ol similar outer olcctronic conligurations
All the elements of group IA (or 1) i.e. alkali
a[tcr cerlain rcgular intqrvals. By correlaling thcsc
metals have the similar outer electronic configura-
t\\,o ()bscrvutions, we can say that
tion, r'.e. nsl where n refers to the number oJ the
Tht caute oJ periodicily in propertics is tha repeli- o[termost principal shell. These electronic con-
fitii of ,similar outer electronic conliguraliotL\ ul hgurations are given below in Table 4.2.
ce rlui n regu lar inlem u ls.
Thus, it is because of similarity in clectronic configuration that all the elements have similar
AR
properties.
C
In a similar manner all the halogens, i.e., elements ofgroup VII A (or 17) have similar outer electronic
S
configuration i. s- /rJz rtps and as such possess similar propirtiei. Thc eicctroiric configurations of halogens
N
and zero. Both these systems of numbering the a seies of elements whose atoms have the same
groups are shown in the long form of the periodic pincipal quanrum number (n) of the outermost
C
table given on page 4/9. sftell. In other words, each period begins with tho
S
N
(ii) The elements ofthe frrst two groups, i.c., filling of electrons in a new energy shell For ex-
IA
s-orbitals whi-le those of the last six groups, i.e.. The lirst p€riod corrcsponds to the filliog of
13 - 18 lying on the extreme right involve the filling electrons in the first energy shell, i.e. n = 1. Since
of electrons in thep-orbitals of the valence sheU. this energy shell has only one orbital, i.e. 1s which
The elements of these eight groups, i.e., L,2, can accommodate oDly two electrol]s, therefore,
13, 14, 15, 16, 17 and 18 are collectively called fint Deriod has onlv two elements.'lhese are
t ydrog.n (rr1) and h;lium (1-t2).
The seconrl period corresponds to the Iilling
of electrons in the 2nd energy shell, i.e. n :
2. Since
this shell has /our o,;bitals (one 2s and three p)
their valence shell electronic configuration is
nsz np6.
(iii') The elements ol groups 3, 4' 5, 6' 7' 8' 9' 10,
1l and 12 are cslled trmrilion elements since lhei the second shell is comPlete.
properties lie beia,een the ProPetties of the reactive The third period corresponds to the frlling of
metak (alkali and alkaline ea h metals) placed ott electrons in the third shell, i.e. n = 3. This shell has
the extreme left and non-metals (lfilogens and chal' nine orbitals (one 3, three 3p and five 3d). How-
cogens :
rxygen fatnily) placed on the oLlreme iqht ever, we know tiom energy level diagram for mul-
of the peiodic table. tielectron atoms (Unit 3) that3d-orbitals have even
In these elements, both the outermost shell higher energy than 4s-orbital. Therefore 3d-orbi-
aDd penultimate shell (next to the outermost) are tals are filled only after r ing 'tr-orbitals' conse-
|1 I
fl
DOWNLOAD FROM IITIANS CAREER
o
F
@
U)
OLDGROUPNOS + B VB V8 VB \ IIB B B VIA VIIA 0 1'I
MODERNGROUPNOS + ,1
2 3 4 5 6 7 9 10 11 12 13 't4 15 16 17 '18
6
I
s-BLOCK (ns1-2; o
LONG FORM
P-BLOCK (nP1-6)
z
o
l'l
383ts8:1"?, OF THE PERIODIC TABLE @ m
+ 1
ns2 np6
r
m
2
E
(1s)
H
Hyd.ogon
1sl nsz
@@(E@o
npl) np2) np3
nsz ns2 1ns2 np4 ,s2 np5
H.
H.llum
'le2
m
z
--.1
3 4 5 6 7 I I 10 U)
a LI B! B c N o F N.
(2s 2p) L hium
2s1
B.rylllm
2s2 d.BLOCK (TRANSITION ELEMENTS) k2
B@
2p1
Carbon
zc2 zi
Nill*n
z"2io3
Oxre$
2s2 zg4
Fludim
2s2 2ps
N@n
2s2 2pG
zo
11 12 [(rl )dl-10 nso-2] 14 't5 16 17 18 -o
E N. M0 AI st P s cl Ar m
R
(3s 3p) Sodluh
o o o o o o o @ @ (D
Slli@ Sulphur Chloire tu9oo
I
EE
3sl L2 an2
19
3s2
20 21 23 24 25 26 27 28 29 30
3s2 3p1
31 JZ
3s2 3p3
33
3s2 3p4
34
3s2 3p5
35
3s2 3p6
36
o
o
E K Ca Sc TI Cr J'N F. Co NI Cu Zn Ga Ge A! Sc Br Kr
6
AR
(as 3d 4p) Pobsium CalciuD S€ndium Iilanium Vanadium Chromrum lrcn Coball Nckel Copp€. Zinc Gallium Selenrum BMire Krypton
4s1 6a2 ca1 t.2 3d2 4s2 3d3 4s2 3d5 4s1 3d5 4s2 3d6 4s2 N7 4s2 3d8 4s2 310 4"1 310 4s2 u2 a"1 k2 12 ,^3 4s2 4p4 qs2 lp5 4s2 4pG
^n2
C
38 39 40 4',1 42 43 44 45 46 47 48 49 50 51 53 54
E Rb Sr Zr Nb llo Tc Ru Rh Pd Ag cd ln Sn Sb T€ I Xe 2
=
S
(ss 4d 5p) Ytu.ium Niobium ldine
Silver
q"0 4d10 5sl
lndium Tin Xercn -u
4dl 5s- 5sl 4d8 5s l 431 0
a
N
5s2 4d2 5s2 4d4 ss'l 4d5 4a5 ss2 4d7 5s1 4d10 5s2 5s2 sp1 st2 sp2 ss2 sp3 5s2 sp5 ss2 sp6
55 56 57 72 73 74 75 76 77 q o
IA
78 79 80 81 82 83 E5 86
E C! Ba
Banuh
L.' HI T. w R. O. lr ft Au Hg TI Pb BI Po At Rtr 1'
(6s (ar) sd 6p) C€sium Ianthenum H6fnlum Tanblum Tun96tff RlEnium Osmlum lddium Plollnum Gold Thallium Loed Bismulh Polonium Asbline m
IIT
Radon
6s1 6s2 5d1 632 sa%s2 soa s* 5d5 6s2 5d6 6s2 5d7 6s2 5d9 631 56105s,| 310 5s2 6s2 6p1 6s2 6p2 os_ op" 6s2 6p4 6s2 6p5 6s2 6p6 I
8l 88 89 104 105 106 107 108 109 110 't 11 112 114 115
-t
a Ft R! Ac" Rf DI Sg Bh X! llr tun m
(7s (50 6d) Radium Ouhium
Uuu Uub uuq uup'
NOBLE
a
7s1 7P 6d'l 7s2 5y'4 6d2 7s: 6d3 7s2 6d ts2 6d5 7s2 6d6 7s2 6d7 7s2 6d8 7s2 56'lo 7"1 6d1 0 7s2 7s2 7p2 7s2 7p3
58 59 60 61 62 63 64 65 66 67 68 69 70 a1
'LANTHANOIDS (4f-series) Ce Pr Nd Pm Sm Eu Gd Ib Dy Ho Ef Tm Yb Lu
Cerium Tertium Erbium Thullium
1+tl-14 SOo-t Os2;
4fl 5d1 tu: 4F sdo 6s, 4F sdo 6s 4r7 fto 6s2 It7 sdl 6s: .P kP 83
90 91 92 93 94 95 96 97 98 99 100 101 102 103
-ACTINOIDS (sf-series) Th Pa U Np Pu Am Cm BK cf E3 Fm Md No Lt
Thorium Cudum
(5P-14 6do-1 7s2) Nob€lium
sP u2 7s2 t,:6dl 7s2 iP 6d1 7s, il{ 6dl 7s: 5F 6do zs2 sf 6do 7s2 it7 6d1 7si 5,9 6do 7s2 910 6do 7s, tf1 6do7s: <4: 6do 7si J13 tuo 7sj 5f{ 6d 7s tfla6d1 7sl
'Dis@ered rct rc@ntly by Ru$ian aDd US scbntist by hining arrcium (Z=95) with @ldum lZ=20) ?@teated in a cyclotron The calciurn nucleus simply tsed into the arrcium nuctous
5
@
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4110
..,1t . t' : Neu, Course t
quently, third period involves the filling sf only four the fillinsof seven 4f-orhitals begins with ceri.um (Z
otbitols (o]ne3s and three 3p) and thus c ot.ltains eiSht = 5o-6i-anaends upwith lutetlum (Z = tl).'Thrsc
e/enrentri from sodium (Z :
11,3s1) to argot (Z = foirteen elements constit,'tc the flr!l,furi0ilqgr
18,3s2 3P6). transition series called lanthanides or lan-
The fourth period corresponding to thefilling thanoiils.These are separated frori the main fiiiic
of electrons in the fourth energy level, i.e. n = 4.lt of the periodic table and are placed at thc bottom
starts with the filling of,tu-orbital. However, after of the periodic table.
filling4r-orbital, the hlling of hve 3d-orbitaLs begins The seventh period corresponds to the filling
since the energy of 3d-orbital is lower than those of ofseventh energy shell,i.e. n = 7. Like sixth period,
9-orbitals but higher than that of 4s-orbital. Fur- it is also expected to contain thirty-two elements
ther, the filling of ,ld and 4/-orbitals does rot occur corresponding to the fi)ltng of sixteen ofuitqb (one
iu this period since their energies are higher than 7.r, seven 5/, five 6d and three 7p). However, this
that of even 5s- orbital. Therefore, in the fourth period is still incomplete and only 28 elemcnts are
period, the filling of only nine orbitals (one 4s, hve knowtr at present. In this period, after the hlling of
3d and three 4p) occurs which can accommodate at 7s-orbital, the next two electrons (i.e., 89th and
the maximum eighteen electrons. Therefore, ftitrth 90th) enter thc 6df * orbital against aulbau pincipk
peiod contoins eidteen elemenls from Potassium and thereafter the filling of seven 5/-orbitals begins
(Z: 19) to krtpton (Z : 36). with proactinium (Z = 9L) and ends up with
The lifth period, Iike the fourth period also lawrencium (Z : 103). Although thorium (Z : 90)
contains eighteen elcments since only nine orbituls does not have any electron in the 5/-orbital, yet it is
(one 5s, five 4d and three 5p) are available for filling considered to be a /-block element. Since its
witb electrons. It begins with rubidium (Z = 37) in properties resemble more the /-block elements
which one electron enters the 5s-orbital and euds
R
than the d-block elements. These fourteen ele-
EE
up with xenon (Z ments from thorium (Z : 90) to lawrencium (Z =
=54) in which the filling of
AR
three 62) are available for hlling with electrons, includes man-made raalioacd\re-dlements. In order
IIT
lherefore, sixth period contains thirty-fivo elemeats - to avoid the undue expansion of the periodic table
It begins with cae.sium (Z : 55) in which one actinides like lanthanides, have also been placed
electron enters the 6t-orbital and cnds up with separately at the bottom of the periodic table
ratlon (Z = 86) in which the filling of6p-orbitals is The number of elements in a period and the
complete. of fu-orbi- tlpe of orbitals being tilled up is given in the
tal, the nff electron (i.e., enters the 5d*- Table 4.4.
and thercafter,
since long while others have been discovered only nounced. The main points of this nomenclature
recently. Although names and slrnbols to many of
C
are :
these clements have been assigned but these are (i) The names are derived directly from the
S
elements have been assigned two nameVsymbols. numbers from 1-9 and adding the suftix iran. A
For example, element vith Z = 104 is called either
IIT
01234567E9
nil un l)i tri qund pent hex sept oct enn
nubtqphsoe
(ii) Iu certain cases, the names are shortened. 4.9. Eleclronic Configuration ol the
For example, bi iwn and tri ium are shortened to Elements and the Pedodic Table ::iii:ii:ii::iilrittiiitii::tit::
IABLE 4.6. Recoruncnded and Olficial names of Glements with Z > 100
120
S
odic table on page 419. However, comPlete electron and this enters fu orbital. The rest of the
N
to be discoveled
"Elemcntsyct
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CLASSIFICATION OF ELEt\,4ENTS AND PEBIODIC|TY lN PHOPERTTES 4113
(v) The compounds of s-block elements with elernents qrc highly stable and hence exhibit very lot ,
C
predominantly ionic.
. . The_elements.of group 17 are called hdegll
N
(vi) Most of the metals of this block impart Gallprodteer.s) wbile those of group 16 are ia-liEd=-
IA
outermost shells is already complete but their aracter increases from left to
respective p-orbitals get progressively filled in by this block.
the addition of one electron at a time as we move .. _ (ii) Their ioni"ation energies are relatively
higher as compared to those ofs-block elements.
from group 13 ao 14, 75,16, 17 and 18. Since these
elements contain one to six electrons in their (iri) They mostly form covalent compounds.
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4114
Pradeep's WD
(iv) Some of them show more than one (uan'- incomplete seventh peiods in wlich tlrc lqst electron
able) oidation states in their compounds. enteni the d-orbitals of their respective- penultimate
(u) Their oxidising character increases from shells are eollectively called d-block elements.
left to right in a period and reducing character yffiineralcharacteristics of d-Block Elements.
increases from top to bottom in a group.
' (i) 'l'hey are hard, malleable (i.e.. can be con-
3. d-Btock Elements. Elements in which the verted into sheets) and ductile (i.e., car, be draum
last electron enters any one of the ftve d-orbitals of into wires) metals with high melting and boiling
their respective penultimate shells are culled d'block points.
elements. Since a d-subshell has frve d-orbitals, (fi) They are good conductors of heat and
each one of hich can acco[rmodate two electrons,
w. electricity.
therefore, in all there are ten vertical columns com- (iii) Their ionization enthalpies are between
prising ten groups of d-block elements, namely 3, 4, .s-andp-block elements.
5, 6, 7,8, 9, 10, ll and L2.
(iv) They show variable oxidation states.
The atoms of the elements belonging to these
(v) They form both ionic and covalent com-
groups usually have 1 or 2 (zero in some cases)
pounds.
electrons in thes-orbital of the outermost shel7,i.e.,
ns-orbital while the electrons are being progres- (vi) Their compounds are generally coloured
sively filled in, one at a time, in the d-orbitals of their and paramagnslis.
respective penultimate shells, r.e', (n - L) d-orbi- (rzl) They form coloured complexes.
tals. Thus, (viii) Most of the transition metals such as !
Cr, Mn, Fe, Co, Ni, Cu etc. and tlreir compounds
are used as catalysts.
R
(u) Most of the transition metals form alloys'
EE
Since the properties of these elements are (x) Zn, Cd and Hg which have the
midway between those of .r-block andp-block ele-
AR
It contains ten elements from scandium to zinc elcmenls.In all these elements, the s-orbital of the
( rrS" - ,oZn) h which 3d-orbitals are being last shell (n) is completely filled, the d-orbitals of
the peuultimate (n - 1) shell invariably contains
progressively filled in.
zeto or one electron but the/-orbitals of the ante-
The second transition series which forms a penultimate (" - 2) shell (being lower in energy
part of the hfth period also contains ten elements
than d-orbitals of the penultimate shell) gets
from ytterium to cadmium (:sY - arCd) in which progressively filled in. Hence
4ri-orbitals are being progressively filled in.
The third transition series which forms a part
of the sixth period also contains ten elements, i'e.,
lanthanum ( srLo) and from hafnium to mercury There are two series of/-block elements each
( rrHf - s.Hg) in which 5d-orbitals are being Threfore, in all there are 28
progressively filled in. periodic table. These are
the periodic table.
The lburth transition series which forms a
part of the seventh period also contains ten ele- Tlrc elements of the first series, i.e., cerium to
ments, i.c., actinium (acA") and elements from, lutetium ( rrC" ,,Lu) which form a part of the
-
rutherfordium (,*RI), to ekamercury or Unun- sixth period are collectively called as lanthanides
bium (Z : Li}).In all these elements,6d-orbitals or lanthanoids since all these elements follow lan-
are being successively hlled in. thanum in the periodic table and also closely
resemble lanthanum (La) in their properties. These
Thus the etements of groups, 3, 4 5, 6, 7, 8, 9,
are also called rare earth elements since they occur
10, I1 and 12 belonging to fotuth, fifth' sirth and the
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CLASSIFICATION OF ELEIVENTS AND PERIODICITY IN PROPERTIES 4l'ls
scarcely in thc earth's crust. In lanthaoides, 4/-o.- Most of the non-metallic solids are brittle and are
bitals arc bcing progressively filled in. neithcr malleable nor ductile.
77tc eletner s of setics,l.c., thorium
rc secottd Thends in m€tallic and non-metallic charac-
to lawrencium ( e6Th ln Lr) which forrns a part
- ter. 'llc-rnetallic character ilcreascs from top -t!
of tho incomplete scventh period arc collectively bottom within a group and non-metallic charaol.er
called actinides or actinoids since all these elc- _r4creases from left to This
ments follow actinium in the pcriodic tablc and also change lrom metallic t er is
closely rcsemblc actinium (Ac) in thcir propcrties. not abrupt as showu by long
In actinides, s/-orbitals arc being progrcssivcly - form of the periodic table given on page 4/9. The
fillcd in. elements silicon, germanium, arsenic, antitnony and
All the actinoids are radioactivc elenrents. tellwiunt (bo
Thc llrsl threc clements. i.L, thorium (Th). ly across the
protoactinium (Pa) and uranium (U) occur in na-- both metals
ture but the remaining 11 elements, i.e, from nep- callcd semi-metals cir mCGII6iili.
tunium to lawrencium ( rrNp - ,nrLr) have been 4.11. Advantages ol the Present (or Long)
prepared artificially through nuclear reactions. ,orm ol the Periodic Table i,,r.,,,
Tlrcsc eleven elemet s are cqlled transuranic or lrsn-
The present form of the periodic table has a
suranium elcments rince tlrcy follote urqnium in the
large number of advantages since it classifics [he
pctiodic tqblc oruL ulso haye been deived. from it
elements on the basis of electronic configurations
tltrough nucleat reoctions.
of their atoms. The important advantages are :
All the/-block elements, r.c., lanthanides and (i) It relates the position of an element in ths
actinides arc also called inner transition elements
table to its €lectronic configuration more clearly.
sincc they form transition series within the transi- R
EE
tion clements ofd- block. (ri) It is easy to remember and reproduce. The
elements ca.n be teproduced more easily in se-
AR
(ir) Their compounds are generally coloured. (iv) The elements are classified trrto tronrul
(u) They have a high tendcncy to form com 13- 17 groups and azn-
plexcs. to 3
- 12 groups on the
nic configurations.
(ui) Most ofthe elements of rhe actinide scries
(v) The elements are also classified as actiyc
are radioactive.
and 2, heavy metals
Metals, non-metals and metalloids. In addi- no,t-nletab placed in
tion to the division of the elements into r, p, d and ps 13- 18) of this pe-
/-block elements, all the elements can be broadly
divided into metals and non-metals.
_ (rz) Based on thei electronic configuration,
letals. Metals comprise 75% ofalt the known p, d arr'l l-
9fe1ent1,h9v9 been grouped into s,
clements and appear on the left hand side of the block. This has helped us to understand their
periodic table. With the exception ofmercury, gal- properties easily.
lium and francium which arc liquids, alt other me- ments of fourtb" fifth,
d sixth assigned properposi-
tiom
I (viii) A satisfactory position has been
s 8- 10 consist-
Non-metals. Non-metaLs may be gases, liquids (Group VIII of
or even solids with low meltiag and boiliog poinls.
DOWNLOAD FROM IITIANS CAREER
4116 Pradeep's
Since tong form of the periodic table corre- 4.13. Prediction ol Period, GrouP
and Block ol a Given Element
lates the position ofelcments to the electronic con-
figuration of their atoms, it is, therefore, nearly an The period, group and block of an element
ideal arrangement. can be easily predicted from its electronic con-
hguration as folows :
4.12. Dciecls ol the Present (or Long)
f orm o, the periodic Table : .:: :.r r.: :: .:: i ,: r: i :j .:i..:.:::..::rl (i) T'\rc peiod ol an elenrcnt conesponds to
tlrc pincipol Emnlrun ntunber of the valence shell.
Although the presetrt form of the periodic (ii) The block of an elenrc t corespottds to the
table has removed most of the shortcomings of ty?e ol oftitol wl'.ich rcceives the last eleclrun.
Mendeleet's original and modified periodic table' (iii) T'lu Sroup oI an elemeat is Predicted from the
yet it suffers from the following defects :
number of electrons in the valence shell orland Penul'
.<:ff?osition of hydrogen is not scttled though timate shell (last bul one, i.e. n - 1) asfollows:
it fias been placed alongwilh alkali metals in (a) For.s-block elem€nt$ gtoup rutmber is
group 1 and halogens in group 17 since it shows eEtal to the n,lumber ofvalence electrons.
many properties similar to both alkali metals and
(l) Forp-lrlockeleme 5 gntup number is eqrul
halogcus.
,o 10 + number of electrons in the Yalence sh€ll.
(ii) Lanthanides and Actinides have not been (c) For d-btock elements, group number is
accommodated in the main body of this periodic
equal to the number of electrons in (n - l) d-su bshell
tablc. + number ofelectrons ln valence shell (nth shell).
R
EE
t.\ \\ ,t.tr 1,1. (s) Wite the electronic con- (c) Classify them as rcpresentqtive elements,
of elenwtls given below : noble gases, transition ond, innet transition elements.
AR
figtuotions the
A (At. No. = 9), B (At. No. = I2)' C (At. No'
C
: 29), D (At. No' = 54), and E (At. No. = 58) Solution. (a) Electronic conliguration of the
S
(b) Also prcdicl the peiod, group number and elenr B, C, D and E are as follows :
N
IA
9 ti x2 zf
B
1t bz zs2 2p6 3s2
D 54 kz zt2 2p6 3s2 3p6 3d1n 4tz 406 47to 5<2 506
E 58 Ls2 Zf 2p6 3rz 3p6 3d1o 4r7 4p6 4dto 5.2 5p6 6sz 5d1 4f
(D) Element A receives the last electron in ]p- Element C receives the last electron in the
orbital, therefore, it belongs to p-block elements
and its group numbcr : 10 + No. of electrons in
the valence shell = 10 +7 -- l7- Further the
period ofthe element = No. of the principal quan-
ium number of the valence shell = 2nd.
Element B receives the last electron in 3s-or- Element D receives its last electron in the
hilal, thereforc, it belongs to s-block elements and 5o-orbital, lherefore, it belongs to p'block elements
its group number = No. ofelectrons in the valence uod it. g"oup nurrrber = l0 + No. of electrons in
rt iit = Z. Further the period of the element = No' the valJnce-shell : 10 + 8 : 18. Further, the
of the principal quantum number of the valence perlod ofthe element = No. oIthe principal quan-
shell = 3rd ium numher o[ rhe valence shell = Sth.
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CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPEBTIES 4117
Element E receives its last electron in the ([) (i) i.e. orygen, (iv) i.e. neon, (u) i.c. siticon
4/-orbitat therefore, it belongs to f-block elements. and (vi) i.e.nitrogen are2-block clements and
It may be noted here that the filling of 4f-orbital (i) Manganese i.e. (vii) is a transition elcment.
occurs only when oae electron has already entered
Sd-orbital. Therefore, element E belongs to f-block
L ,.' ii
.i !.Predict the positbn oJ thc clc-
el€m€nts and not to d-block cleneDts. Since it meti in the peiodic table sotisfying tltc clectronic
belongs to lanthanide series t-herefore as such it configuotion, (n - l) dt ns2 foru : 4.
does oot have atry group number. However, its (N.C.E.R.T)
period : No. of the principal qua-ntum number of Sulution. Forlt = 4. the elec(ronic configuru-
the valence shell = 5th. lion =-J4=l) 71 4s2 = 3d14s2. Thc elcmcnl- cor-
(c) Elements A atd, R arc representatiee ele- responding to this configuration is scortditun wlticlt
raezrs since their last electron entres p- and s-orbi- is a d- block element.
tal respectively. Group number = No. of electron in (a - l)
Element C is a transition element sincr it d subshell + No. of electrons in the nth hell
receives its last electron in the d-orbital. :7+2=3
Element D is ap-blo ck element
'.ith complele- Il\ \\ll'r.l 1.1. Elcments A, B, C, D ancl E
ly filled s- andp-orbitals of the valence shell. Such have the following electronic cottfigltto lhns.
a type ofp-block element is ca-lled a noble gas.
A: 1s2 2s22pt
Element E is an ,nn er transition element siace B: ls22s22p63P3pt
it receives its last electroa.it the f-o,bital.
c:1s22i2p63s2Jl
.The electronic configuraion of
some ven below :
D: I s2 2s2 2p6 3s2 3f
R
E:1s22s22p63s23p64s2
EE
(i) 1s2 2s2 2p1 (i) ltz zsz zp6 3st
(iii) W4tich among these will bclong to tlte sunrc
AR
. (f) (i) i.e. orygen, (iv) i.e. neon and (ra) i.e.
nitrogen belong to 2nd period
alkaline carth
configurution
€) (ir) l.e. neon beirg a noble gas has lowest
7 p6 8sz or
reactrylty lement with z
= 118 is Uuo.
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4118
l. Write the names and atoDlic numbcrs ofthe lollow- State to which blook of lhe periodlc table each of
lDg clements :
lhese elemerts belongs.
(i) The tburth alkali metal 3. An elemeDt 'X' with atomic nur,lber 112 has
recently been discovered. Predict its clectroniccoD-
(ii) The lhird alkaliDc earth metal figuration ancl suggest the SrouP in lvhrch this ele-
(,ii) The tifth element of the first transition series ment rvould be placed.
(iv) The tirsl lnner traDsitio[ elemeDt afld 4. Arrange the lbllowing eleD'lents il1 the incrcirsing
(v) 'l}le sixth uoble gas. order of nretallic character : B, At, M8, K
tN.C.E.n.r)
2. Ths outer electronic mnfiguration oi some ele-
lnents are given below : 5. W'ite the electro[ic configuration aDd tbe block to
which an element with Z = 90 bclongs.
(i) 3p3 (ii) 3(15 ,\t 1iii1zt2
3s2 3p6 +t2
6. How do the electronio configurations of the elements
(iv) 511 6e2 Q) 4f1 5dr (,,t1 with Z= 107 109 differ fiom onc arother'l
-
S EC-TION_II
S
N
AI'OMIC OR I'ERIODIC
IA
PROPERTIES OF ELEMENTS
IIT
= 1.602 x 10-re J pcr atom (t cal : 4.184.1) third ioniaton onthalpies respectively.
C
: rnol I
23.06 kcal
IA
1023 .1
The successive ionisation encrsies of somc
= 96.49 k.l mol-1 elcmcnls (in kJ mol- I 1 arc given in Tirhlc -1.7
H 1312
l,rl
He 112 2312 5250
Li lt2 zsl 520 7zvt 11810
Be 1r2 2r2 899 175't 14850 21000
B 7? z? 2p1 801 un 3638 250 3?l24
C 1.t2 2r2 2pz 1086 x52 4619 6220 3'1820 4',1280
N 1tr2 2t2 2oz t40z 2a58 4516 7413 9443 5325-5 6432u
o b2 zr2 zp1 t3t4 3388 5296 7468 10987 t3323 ri40-54
F lt' l68l
tsz 2.tz 33'15 6045 8408 1rc?n 15160 17564 92012
Ne \t2 2P 2p6 2080 3962 6226 9361 12186 t5236
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4l2O
Neul Course
It maybe seen that,IE, is alwalt greater than which will hold its remaining electrons even more
energy required to remove
IE, and IE, is always greater than Iq, and so on
e gaseous atom should be
l€' IE3>Iq>IEl required for the second
Explanation. This may be explained as follows: be greater than IQ. Thus,
R
EE
AR
Therelativestabilitiesofvariousoxidationstatesofanelementcanbeeasilypredictedonthebasisoftheir
halpies.Il lhe dwfence in ionizalion entlnlpies of two succet\ive staleN is aPprc* eEul
e
C
successive ionization
ll or let, the lower oxjdation state ir hot ttable. conversely, if the
S
diffetence
IA
te, = SZe U mot-1,I% = 1?95 kJ mot-l,IE3 = 2758 kJ mol-l and IEn = 11580 kJ mol-1'
IIT
rhat ofIEa _ IE3 is much more thaD 1450 kJ nrol-1, therclorc, + 3 oidation State ofAlitthemo stoble.
l.lx,ltr\ll{,E ;1.6 calculate the energ required . . Total amount of energy needed to convert
to convetl all the atoms ol magnesium to iagnisium Mg @) atom into Mgl+G) ion = IEr +IEz
ions present in 24 mg of magnesium vapours ? First
andiecond ionimtion enthalpies of Mg are 7i7 76
= 731 76+ 1450'73kJmol-r
urd 1450.7i kl mot-I respectivety. = 2188 49 kJ mol-1
)4U
ces
Accordi.trg to the defiaition of suc-
n energies.
24 mg ot Mg =
f.O t = 10ffi ^ot.
IEr ._
Mg+@)+e-@); = 10-3 mole
IEr = 737'76 kJ mol-l . . Amount of energy needed to ionize 10-3
Mc* G) + IE; ........ Me+ @) + e- (s) i mole of Mg vapours = 2188 49 x l0-3
IEl = 1450 ?3 kJ mol-l = 2.18t kI.
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CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPEBTIES 4121
H INlfS FoRDtFFtcuEr
No. of moles ofNa present is 2.3 mg ofNa
"RortElvs
= 0 0417 x 740 = 30.83 kJ
23xibi0
11xlf Ener!5/ feft unused = 50-30.83 =
= ro =1 x l0'mole 19.1'1 kJ
Nqw 19 17 kJ witl be used to ionize Mg+ G) to
..,Required eDergy = I x to-a x 495 x ld Mg'* G)
= 49.s J
2. Required energ)' = 0 1 x 13.60 x 96 49
.. No. of nroles of Mg+ G) mnverted iDto
RMg2* G) = tg 1'.,11450 = o ot32
EE
= l3l 226 kJ
3. Required energy = t x (24 58 + 54.4) x No. ofntoles of magnesiunl ions left as Mg+ G)
AR
96.4g
= 7620.1AO kl. = o.o4l?-4 0132 = O.t2A5
C
4. No. of Doles of Mg vapours present in 1 I = lZ4 .. %age otMg+ tg1= (0.028s,/0.0417) x 100
S
= 0 0417
N
= 6a 35qa
IA
of Mg k) ro M8+ k)
4'14.4.Factors Governing the Ionization Enthalpy. Ionization enthalpy depends upon thr:
-
factors:
following
s>P>d>f
AR
"
Obviously, if the pcnetration effect of the
C
R
EE
AR
--+
N
l**
i
Ne
R
EE
simultaneous decrease in atomic radius, the o.
AR
valence electrons are more and more tightly hcld (ii) The removat of an electron ftom O gives a
by right in .a
C
rl9 ce lontza_
while this is not so in case of N, i e N+
IA
l.). 1\ I l'!,1,. t.7 The electronic configtratiotr Since the M-shell is more distant from the
N
for the following neutral atoms are given for use in nucleus than L-shell, so lesser amount of energr is
IA
(a) lsz , h2 ,2p6 ,3s2 ; (b) Is2 ,2sz , 2p6 , 3s1 ; from the L-shell. In other words, ionization enthal-
(c) lsz,h2,2p4: (d) ts2,2s2,2ps; py (IE) of atoms (a) and (b) shoutd be lower than
that of atoms (c), (d) and (e).
(e) 1s2,2s2,2p6.
Further, in case of atom (a), the electron is to
(i) Wich of tlrc electrcnic configuratiott givet
be removed from tbe more stable completely filled
above wouldyou expect for the noble gas ?
3s-orbital whereas in case of atom (b) it is not so.
(ii) Wticlt of lhe elecIonic confrgurotions given Therefore, the IE of atom (D) should be lower than
obove wortld you expect to ltote the lowest ionization that of atom (a).
enthalW.
The nuclear charge on atoms (c), (d) and (e)
(iii) List the above configurations in order of is +8, +9 and +10 respectively. Since the IE
i n cre o s ing ionization enthalpy. increases withincrease in nuclcar charge so theIEs
Solutlon. (i) Arrange the electronic con- of atoms (c), (d) and (e) follow the sequetrce:
hguralion o[7ll the atoms in order of increasing c < d < e.
atomic number in such a way that atoms containing From the above discussion, we conclude that
tho same outer energ5r shell are group€d together. the ionization enthalpies of the fivc atoms increase
Thus, we have in the following order :
1:7 zrz 2p4 l:2 2ps
2s2 b2 %2 2p6 b<a<c<d<e
(.) (d) (")
...L-shell i.e., Lr? 'b2 2p6 k1 < b2 2s2 2p6 3s2
L\2 'b2 zp6 k2 1s2 2
zp6 at1 ...M-shell . 1", b, Zp, . 1", 2"" d . 1", b, bo
(,) (6)
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4126 Ner4 CouYse Chentist !
(ii) Evidently, atom (b) with elcctronic con- (d) a metqt lhatJotms a stable binary halide of
figuration, Ltz '2s2 2p6 k1 has the towest ionization the fonnul& AX2 (X = halogen). (N.C.E.R.T,)
enthalpy.
(ri) Since the outer electronic conhguration l;:tl"":
of ncble gases is ns2 np6, therefore, the electronic is fikely to
'!:2 2s2 2p6
conlrgura-tion, [atom (€)l represents an
noble ga-s.
(b) Since the IE1 of element IV is very high
I,lx-All!'l.l- +.s nu fint (IE) qnd tlrc second
and its IF., is not so high (actually almost double),
(IE2) ioniz(ttio,t enthalpies (kJ mol-i) of a few ele'
it is likely to be a rec ctive non-metal (i.e., a halogen) .
men$ (lesigruted by Ronwn nwneruls ore sltown (c) Among the elements listed,IE, of element
bektw :
Element IEt lE, I is the highest and its IE, is also not so high,
therefore, it must be a noble gas.
I 2i72 5251
(d) The IE' of element III is higher than that
II 520 7i00
of element II, but unlike element II, its IQ is only
Irr 900 1760
it is likely that ele-
jiEq about twice its [El, therefore,
u t6t]0
ment III has two electrons in the valence shell (i.e.,
Whiclt of the above elements it likely to be
skaline earth metal). As such it will form a stable
(a) a rcsctive metdl (b) a reactive rtttn-metol binary halide of the fornula AX, where A is the
(c) a noble gas metal and X Ls the halogen.
R
EE
AR
C
l Arrange tbe following in the order of iocreasing 5. For each of tbe follclwing pairs, Predict which one
lower first ionization enthalpy
S
bas ?
ionizatron enthalpy :
N
(i) 1t22rz lsz (ii) ls? 2 2p6 3sr (i) N or o (ii) Na or Na+ (iii) Be+ or M82+
IA
2p6
(ii, h2 2t2 2p6 (iv) I or I- l^ns. (i) O, (ii) Na, (r ) Be+ (lv) I I
IIT
t-tz 2t2 416 *2 (D and Na, b2 2f2 2p6 3rl (n) bave (a) In casr ofNa+, an electron ltas to be lost fron'l
loc/E{ IEI than q N, O. Out (, and (ii), (i) has higher a stable inefi gas coDfiguration but it't cilsc of Na,
IE, due 0o higher nuclearcharge and cornpletelyfiled loss ofan electron gives stable inert gas configura-
tion.
r.orbital. Thus, the overa[ order of inqeasiDg IEl is
(n) < (t) < (rv) < (y) < (rli,). (6) Na is neutral but Na+ is +!ely chargeci.
2. (aHrv) has highest IEI due to srable emcrly half- (iii\ Be+ hat lower I E', tlnn Mq2* hccitusc in case
filled electronic configuratioo. (DHi r) has highesr
of Be+, the loss of or]e eleclroD givcs a stablc iDert
IF2 since the second electron has to be remorr'ed
configuration but rn case ofMgz+, the electron
from the stable exactly half filled electronic con- -[as
has lo be lost fronl thc stable tnert gas contigura-
figuratio[ lefl after remo,/al of Ist electron, ie.,
tion
IE. IE
tr z? zpa t? lr2 d J (iv) I hat lowet IEr than 1- because in case of l-,
-i highest Iq since
(c){i) has the rhe rhird etecrroD an electroD has to be lost front a stablc inert gas
has to be remor'ed from the stable inefl gas con- configurahon.
IF. IF.
l?2? --; --: k"^ -,
IE,!
R
6. (a) IEr ot elenrcot III is rhc highest of rhc rhree
EE
fiSuration, B2 zst
elements listed, thereforc, il is a non-tnetaL.
(d)-(r'i) has the highesr IE1 sinc€ the fourtll
(6) SiDc€ IE ofelement I is very trigh Ns coorpared
AR
itla period, alkalimetal has the lowest and inen gas 7. (a) C has hiBber IEI rhaD B because oI higher
has the highest IEl, therefore, K bas the lowesr Duclear charge.
IEt and Kr has thc highest IEl. (D) N has higherIEr thirn O becausc in cdsc ot N,
4. (, Because of the bigger sbe and stronger sbielding the electroD bas to be lost from a morc srablc
effect, Cl has lo er IEr thaD E exaclty half-fi lled eleutronlc conlidurctirr.t.
(c) Ne has higher IEt than F because ofsta btc inert
(r'i) Among S ard Cl, S ha6 tower IEI due to bigger
gas configurarion.
size and lower Duclear charge,
(ri) K has lower IEl tban Ar because K has one t. (.r) E O. N allbelong lo znd period. Antong lhcse,
F has the highest I Et because ( rfiLs solallesr size and
more electron than Ar and hence can easily 16€ this
highest nuclear charge.
electron to aaquire stable Ar has mnfiguration.
(D) Mg, P, Ar all lie in the 3rd period_ AmoDg these.
(iv) Xr because of its bigger size aod stronger Ar has the highest IEI because it has stable xlert
shielding effect has lower IEI than Kr.
gas configuratioD.
5. (i) O has lower IE r rh4n N because iD case of O, loss (c) B, Al, ca all lie io group 13. B has rhe highesr
of an clectron gives O+ which bas stable exactly
IEt due ro its smallest size.
Electron gain enthalpy oJ ot element mty be defmed second and higher electrongain enthalpies are also
os the energ relatwl when a ncufialisolded gltilttt possible. However, after the addition of one
dlom uccepl\ un elra elslron lo lorm lhe gascous electron, the atom becomes negatively charged and
negative ion, i.e., anion. Il is dcnoled b! L"s H. the second electron is to be added to a negatively
charged ion. But the addition of second electron is
This process may be represented as : opposed by electrostatic repulsion antl hence the
x (c) +e- ""--, X' (E) i enety hos to be supplied fot the addition of second
ncutml Saseous atom electron. lhus the
ariT'L., H . 1,y an element is po
electron is added
Evidently, greater the arnount of energy
energy is released. But when aqother electron is
released in the aboveprocess, higher is the electron
gain enthalpy of the element. added to O- ion to form C)2- ion, energy is ab-
ln oth er words, the electron gain enthalpy oI an sorbed to overcome the strong electrostatic repul-
elemmt is a meastre of the firmness or strength h)ilh sionbetween the negatively charged O- ion and the
which an extra electron is bound to it. Like ionization
new electron being added. Thus,
enthalpy, electron gain enthalpyis measured either First electron galn enthalpy,
in electron volts per atom or kJ per mole. o (s) +e- 1"1 '-"'(s);o-
Depending upon the nature of the elemenl the AH"' = 141kJ mol-l
- (EnaE/
process of adding an electron to the atom can be releatu,
is
eithier exothermic or endothermic. For majority of the Second electron gain enthalpy :
elements, energy is released when atr electron is o-(s)+e-G)+ o'?-G)'
AH"' = a 780 kJ mol-1
(Enet absotb.d)
R is
EE
Similarly, the second elecEon gain enthalpy of
S is also positive. Thus,
AR
is rcleasctr)
principal quantum enerry lewl thereby producing
IA
ct(s) + e_ .,_
ftno -o,_,
is relessed when i'55 g of chloine is converted . .
Energy released when l mole ( : lJ.J g)
completely into Cl- ion in the gsseoLt stsle. of chlorine atoms change completely into Cl- k)
Sotutlon. According to the definition of
=3491rJ
elect nthalpY.
.In ma.iority of the text books, thc negativc of thc cnthalpy changp accomPanying thc addition of an clectrcn
to an isolatcd
g"""orr" i. o'.fin"d as .tccaron 6m ti(A"). Thc ctcctron irfinitfis said to be 'oslllv., il arcr&l is tclcoscd whcn dn isolat d
"to,i
gt,],cous otorn acccpi on ctectron dnd it is osighed a n gald,v. slg3rt if eneryl is to bc wPlied to odd an exlfa
dectort to the isolnlcd
i,ruseoreratom Thii is, hollrclrr, contrary to th; thermodynanlic con!€ntion. Further, since electron affinity is de{incd at absolutc
;ero, thcrcforc, at any othcr temperaturc heat capacitics instead of elcctronaffinity of the rcactents and Produc6 should.bc
considercd. TherEforc, in vicrr o] thesc tso ncasons, the term clectron gain enlhalpy is used instead of
clcctron_affinity
be explained as
C
follows :
S
N
lows.
IA
IIT
below :
bromine to iodine.
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CLASSIFICATION OF ELEMENTS AND PERIODICIry IN
PROPEHTIES 4131
I gso
I
z^
2i325
d>
z=
Y
F
soo
..(ri) enthalpy olnoble gases k
o
tr.l
r (-2es) pos ,vc. e fact that the atoms of
these ele letely fiJlcd subshelJs. As
9173553 a result, in their valence orbitals
ATOi C NUMBER (4 _______)
and the additbnal electron has to be placed in an
orbital of nexldgher shell. As a resuli energr has
FIGURE 4.5. Variation of electron to be supplied to add on additional electrl-n. In
gain enthalpies of halogens.
other words, lhe electron gain enthalpy of noble
gases is positive. Further, as we movi'down the
group, the size of the atom increases and hence
electron gain enthalpies have lower positive values.
For example, electron gain enthalpyof Ar ( I 96) is
lower than that of Ne ( + I l6).
R
EE
AR
C
S
(i) [Nel 3s2 3p3 (ii) [Nel 3s2 3p4 (iii) INel3? jps
(i)NorO (N.C.E.R.T)
(ii) F or Cl (N.C.E.R.T)
ES,CI,F
(N.C.E.R.T.)
given a'oms into dif-
lere order of increasing
atomic nurnbers :
GrouP No. 15 76 1'7
2nd Period F
enthalP".
3rd Period P S Cl
has
3. Which ofle (atom/ion) in the followiDg Parrs
l.'- Arranre the elemenls wilh the folloxing eleclronic
higher electron gain enthalPY'l
.""it""u.ntiona in order oI lncreasing electron Eain
entha"lPy. (i) o-, s (ii) o, s- (tiD o- , s- (it') N- ' P
(i) b2 ztz 2p5 OD \2 ztz 2p4 Qii)82 2] 2p3
I .' - (DO- > S(i4s- > o (iii) o- > s-
(iv) N- > Pl
(tu) b2 2t2 2P6 3? 3P4
FOROIFFICULT ?RObLE*N49
N
IA
of atom is co'tsidered
i:i:ii:;:ii::iiilil:lit:riiii:iii:i::iiiiiiiili,Il:llgliixii:irliiji:iii:l:l:l:
to given bY the radius
4.16.1. size of an atom, i e'' the
Dcfinitton.The
'4 lonwn as atomlc
atomic.size is a vcry important property of an atom ra
since many other physical and chemical propemes
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CLASSIFICATION OF ELEMENTS AND PEBIODICITY
IN PROPERTIES 4133
The distance lrom the centrc of ,he nudctlt to thc For enmple, the internuclear distance be_
oukrmost shzA containing rht electmns.
Or
The distance trom the centre oJ the nutler$ ,o
thc
point upto which thz dewity o! the elqtron cloud
(i.e. prohability of finding the elqtron)
k mari-
mum.
(6) van der lVaals, rartius.
4.162. Difliculties in determining atomic
radius. Atomic radius cannot be delermined It is dqlitd as om-W thc .Iistarce betueen tlz
precisely due to the following reasons :
nucw o! tvo lderticsl twn-hondei! isolttd stot tt
R
EE
AR
derWaals'radii.
o{ atomic
- -orbitolt 4.7 ' OverlaPping
FIGURE
to fotrn u tolalent bond
R
EE
AR
C
S
N
IA
IIT
van
Out of the threc typcs of atcmic radii(covalent'
and hente atomic radius ofan atonl s us
cleternrine
'fhe aiom rc usuallY exPress
number of
iil;;;; Dtry a
ius of xenon can
pr"pared.
covalenL radius.
Thbl'e
4.16.5. Variation of Atomic Radli in the Feriodic with i?u:!u i,?
ovalent or ean det Wsah' decrease
the atomic (covalent) raqr
ior example, consider
. 4.8).
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CLASSIFICATION OF ELEMENTS AND PEBIODICIry
IN PROPERTIS
4135
u (152)
t '|
g
1 20
f Be (11r
o- )
(r '| 00
o B (EE)
I c (77)
N Os)
o
F (72)
(741
246a
AToMlc NUMBER (a--+
R
EE
FIGURF 4.a. Variation of atomic radius with
AR
atomic "'
number across the second perioJ.
C
period
a period.
(ii) The halogens which ue prcsent at rhe
ex- N, O and
trcnte ngl olthe peiodic table hqve the smollest
size. tively.
300
2so
|
K (231)
zoo
E
f, rso
E
o 100
o--
=
0ffi6-;6-uo 60
ATOMIC NUMBER (Z) ------->
R
EE
AR
C
S
N
IA
IIT
ttl
t.----+
'INTERNUcLEAR
DISTANCE
than that ofits par€nt atom. A cation is formed by tion hy the nuclcus on lhc clectrons increases (i.e.
cffecl it'c ttucleur ch trge increases) anrJhencc the sizc
loss of one or more electrons from the neutril
gaseous atom. This generally causes the removalof
oI the atom decreascs. Thus, in nutshcll,
the whole of the outermost (valence) shell of catitn is always smallzr lhun that oJ
The size oJ a
electrons, correwndinq slom due to (i) decrease in lhe
e.8,, Na .-..-.....r Na+ + R
lh.e
number o! shells (ii) increqse in lhe e[fective
EE
c-
1s2 2spz 2p6 3s1
x2 zp6 nuclear charge resuUing in geafer lorce oJ altrac-
AR
ts2
Due to the removal of the valence shell, the tion by the nucleus on thc clectro$.
C
Atonl I.i Na K Be Mg Al Mn
Atotnic raclii (pm) I tSz 186 2i1 1 160 143 126
Crne:ponding cationt +
I Lr+ Na+ K+ Be2 Mg'* Al3+ Mn4+
l,,nt nt,lii llttttt j r,u 95 133 39 65 -50 16
Variation of ionic (cationic) radii within a decreases (i.e., effective nuclear .r).
Hetrce the elecoon cloud of the In
other words, the distance betwoe he
nuclcus and the last shell that contains electrons
increases thereby increasing the ionicradius. Thus,
^9, o
is 133 pm.
(D) The radius of the anion is always larger
than that of its parent aa(rm. An anion is fonned
when a neutral gaseous atom gains one or more ANION
electrons (Fig. 4.12). This increases the number ot
17 ELECTRONS lE
electrons in the anion while its nuclear charge +17 NUCLEAR CHARGE +17
iemains the same as that on the neutral atom. Sinie
the same nuclear charge now attracts greater num-
99 pm SIZE 181 pm
The size oJ an anion is always brger than the corrcsponiling ulom mainly becausv of decreuse in lhe efrective
nucbar charge i.e. leser force of attmction by the nucltttr on lhe el$tror"\.
This is illustratetl in Tahlt 4.15.
Variation of ionic (anionic) radii lvithin in Thus, nitride ion (N3-), oxide ion (o2-),
group. Lik covaletll rudii, the ionic rudii of anions fluoride ion (F-), neon (Ne), sodium ion (Na+),
also increase as we move down the group pimaily magnesium ion (Mg3+) and aluminium ion (Al3+)
due to an increase in the number of shells. For are all isoelectronic species since each one ofthem
example, the ionicradii ofF-, Cl-, Br- and I- ions contains 10 electrons but different nuclear charges
are 136, 181, L96 and 21.9 pm respectively. of + 7, + 8, + 9, + 10, +tl, + lZ aad * 13 respec-
4.172. lsoelectronic ions or species. tively.
. Iis the difroent elnntnt J vhich hwe thp scrae
oJ Variation of ionic size among isoelectronic
nanibt o! ewrons bw ilitsat
mognit& of fla ions. Within a series of isoelectronic ions, as the
nucbr &arye w calld lsohlccftolrlc lons. nuclear charge increases, the force of attraction by
R
the nucleus on the electrons also increases. As a
EE
For example, sulphide ion (S2-), chloride ion result, ionic radii decrease.In other wotds,lhe ionic
AR
(Cl-) and potassium ion (K+) are isoelectronic rudii oI isoelectronic ions deueose with the increase
ions because each one of them has 18 electrons but
C
+ 19 respectively.
N
Besides ions, a neutral atom may also have electrons but their nuclear charges vary i.e. these
IIT
same number of electrons. For example, besides are +7, +8, +9, + 11, + 12 and + 13 as showr in
S2-, Cl- and K+ ions, argon (Ar) has also 18 Thble 4.8. Therefore, their ionicradiiincrease in the
electrons. Therefore, Ar is also isoelectronic with
order:
S2-, Cl- and K+ ions. In order to cover all thcse
species, the term isolectronic species is used. Thus, Al3+ < Mg+ <Na+ < F- < 02- < N3-.
lsoel€ctronic speci es may be delined as neutral This is illustrated in Table 4.16.
or ionic species which have tlrc sante number of
electrons but different ttucleat charges .
The ionic size of isoelectrionic species can be easily conrpared on the basis of their atomic Dumber/number
of
electrons, r'.e. 7tre rutio. Sm4ller the val e of Zle, lorger the izz of the
ryecies. For example,
Ion Z zle lonic radlrrs (pm)
N3- 1 l0 o.'t 771
o2- 8 10 0.8 l,!0
F_ 9 l0 0.9 136
Ne 10 l0 l.o 112
Na+ 11 l0 1.1 95
Mg'* t2 10 12 65
Al3+ 13 l0 13 50
(vii) Ne.
(iii) Caz+ (iv) Rb+
S
(N.C.E.R.T,)
Solution. The number of electroDs in these
IA
2. Arrange the following in order of increasing radii ? lADs.(4) o (r) Sl+ (c) cU
(Ju) Li+ and Na+ both belong to Sroup 1. Bccause ioDic radius ot s2- is bigger than those of F-,
S
of greater number of shells (2 in case ofNa+ aDd 02- and N3- ions. Thus, the overail order of
N
Li+.
the size increases as the magnitude of negative
(v) As has four shellswhile P has three. Therefore,
atomic size ofAs is hiSher than that ofP. charge increas€s : Therefore, among O, O- and
(u) Na+ and Mg3+ are isoelectronic cations. 02-, O has the smallest radius.
Therefore, due to lower effective nuclear charge, (b) Although SP+ has I<I gas configuratioD (I.e.,
ionic radius of Na+ is higher than ihat of Mg2+. has four shells), but K+ has Ar gas coofiguration
2. (i) Size of a cation is always smaller while that of an (r'.e., has three shells), nevertheless ionic size of
anion is atwals bigger thaD the ncutral atom, t.e., Sf+ is smaller than that of K+ obviously due to
I+<I<I-. higher nuclear chargewhich outweiShs the effect of
an additional shell.
(O C and N lie in 2od period while Si and P lie belo$'
them in the 3rd priod. Since elements in the 3th
(c) Si, P and Cl all belong to 3rd period. Since
priod haw higher atomic size than tbce in the 2nd
atomic size decreases as the nuclear charge in-
creas€s. Therefore, Cl with the hiSbest nuclear
period, thercfore, aiomic radii of Si and P are higher
charge has the smallest radius.
than thce of C and N respecrivEly. Since atomic radii
Summary of the Tlends in the Periodic Properties of Elements in the periodic Thbl€.
Alomic radiid6creas6
.q Non l\,4etals
I
.9
E -g
Transition metals z
4.17 .
S
Groups - 1213 14 15 16 17
J Periods
Iiormulae oI ) LiH cHr NH: Il2o HF
hydrides 3 J\AH siHl PHr HzS HCr
4 Ktl ftHl aHr H2Se HBr
5 RbH SnH. SbH3 Hzft HI
Formulae 2 LizO BeO BzO: COz
of oxides 3 NEo MgO AzO: SiOz
4 K2o CaO G%Ot ceoz
5 Rb2O SrO Itlzo3 SnO2
6 CEO Bao Pb02
(D) Variation in a group. When we move one while all the elements ofgroup2 (alkaline earth
down the group, the number of valency electrons metals) exhibit a valetcy of two.
remains the same, therefore, all the elements in a Noble gases present in group 18 are
goup exhibit the same valency. For example, all the zerovalent, i.e,, their valency is zero since these ele-
elements of group 1 (alkali metals) have valency ments are chemically inert.
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4142
I,l\Al\lPLL l.16. Predict tlw fomrulae of the (d) In the 7th period, the 4th transition series
stqble binsry compounds that wouldbe lormedby the ends at element with Z : lLZ, aherefore, filling of
following pairs of elentenfi. 7p-subshell will begin with element Z
Hence, element wrth Z = 114 witl have two
= 113.
(a) silicon and orygen (b) ahtminium and
bromine (c) calcium and iotlitrc (d)element l l4and electrons in 7p-orbitals and two electrons in 7s-or-
fluoine (e) element 120 and oryge,t. (N.CJ.R.T,) bital. In other words, the element z: 114 will lie
Solution. (a) Silicon belongs to group 14. It in group 14 and hence its valence
= 4.
has four valence electrons and hence its valence :4 Fluorine belongs to group 17 with seven
oxygen belongs to group 16. It has six electrons in valence electrons and hence its valeqce
the valence shell and hence its valence = 8-6 =2. =8-7=1.
Therefore, the formula of silicon oxide = SiOz.
Tterefore, formula of compound formed by
(b) Aluminium belongs to group 13. lt has element 114 and fluorine is MFn where M repre-
three electrons in the valence shell and hence its
valence:3. sents the element.
Brominc belongs to group 17. It has seven (e) The 7th period will end at element with Z
electrons in the valence shell and hence its valence = 118. Therefore,filling of 8th shell i.e. 8 s-orbital
= 8-7: 1. will begin with elemell.Z = lL9 and consequently
Therefore, formula of aluminium bromide element with Z = 120 willbelong to group 2 and its
:AlBr:. valence will be = 2.
(c) Calcium belongs to group 2. lt has two Oxygen belongs to goup 16 with six valence
electrons in the valence shell and hence its valence R
electronsandbenceitsvalence : 8 - 6 : 2.
EE
: 2. Iodine belongs to group 17. lt has seven Therefore, formula of compound formed by
valence electrons and its valence = 8-7 = l. :
AR
1. Predict the formulae of the slable binary com- 2. Prcdict the formulae of the stable binary c-om-
pounds thatwould be formed lry the followinS pairs pounds formed by the following pairs ofelements :
1 Afulition offnt electron to a ne trdl alont ir at energic process whle tlut ofrccond elecfo, it rzz endo€rgic Proc€ss.
Q LWor d yorr r€gs,rd Zi <Z = $\Cd (Z = 4t)andIIC(z =t0) ss-s. ord-b:ock elements ? Cive reosors for
yo t answer.
Atrs. The la.st electron in Zr, Cd and Hg enleE the 4.r, 5r and tu-orbitals respectively. Tlrcreforc,on the batit of type
of orbital being fUed" Ese lhree elernenh sltould be rcgarded. as s-block elements. But thc properties of these
elemelts resemble more the d-block rather than J-block elemeoLs as listed below:
(i) Zn, Cd and Hg like other d-block elerDents form complexes but,r-block elcments usually do nor.
(r'i) Zn, Cd and HB like other d-block clemeots form maDy covalent compouDds whereas r-block elements
form ooly ionic compounds.
(iii) Like other d-block elements, the [i6t ionizalion eDergies of Zn, Crl aDd Hg are much higher than those
ofthes-block elements of the same period.
(iv) Like other d-block eleme[Ls, the atomic radii of Zn, Cd and Hg are much lower lhan those of ther-block
ele ments of the same period.
(v) Like otber d-block elements, the electrode potentials ofZn, Cd and Hg are much lEss negative rhan those
ofJ-block eleme[ts of the same period.
Fiom the above discu ssion, it is cleor that the properties of 'Zn, A and Hg resemble more the d-block elements
rather than the r-block elements-
Fhrther, to make the periodic classincation of clemenLs more rational, it is better to study tltem along with the
d-block elements.
Q 2How many elemenb caD he accoEDodated in ihe pEsent set up ofthe lotrg foru ofthe p€riodic talrle? BplalIL
R
An6. In the present set up of the long form of the periodic table, we have seleD periods (ie., principal quantum
EE
Dumber, n = 7) and four blocks (r, p, d- andf-block elemeDts). Thereforc, the maximum number ofelements
which can be accommodated in tbe prescDt set up of the long form of the peri(dic tablc in ac.cordaDce with
AR
Q,3. Crn an element with atomic nurrber 12,6, ifdiscovered, ie accommodated in ttre pre6ent set up ofthe lorg
N
Atrs. No. The maimum numb€r of elemenb which cao be accommodated in the present set up of the long form
IIT
of the Periodic table is 118. Thereafter, filling of 8r{rbiEl shall begiD which will accommodaie ooly two
electroDs. After &-orbitals, the filling of sg-orbitals will begin. SiDce we do Dot havc any prcvisio[ for g-block
elements in the present set up of the long form ofthe periodic table, thercfore, ao element with 3tomic oumber
126, if disco\rered, cannot be accommodated in the prEsent ser up of the IoDg form of the periodic table.
Q. '1. What would be lhe rtomic nuEber ofthe rext (0 alk li lrelal (ii) alkaltne earth metsl (ii, hr.lo8en and (iy)
irert g8s, if dlscoYcrcd itr future ?
Ars. (i) The ocxt alkali metal, if discovered will, have to be placed io the eighth period and heoce its ouer electrcDic
coofi Suration will be &l - Therefore, its aromic numb€r will be (1 t8 + 1) = I 19.
(r'i) Similarly, the next alkaline earth metal, if discovered, will havo &2 as its outer electroDic configuration and
hence its atomic number will be (118 + 2) = lm
(ai) The next haloS€D, if discryered, willhave 7s2 7p5 as its outer eleatroDic configuration. Since the lilling of
7P-orbitals will begil after 6d- orbitals and up to 6d-orbitals, i[ ac{ordaDc€ with Aulbau principle, we can
actommodate oDly 1 12 elemeDts, t he refore, the atomic number of the next halogcD, if discovered, will be ( 1 12
+ 5) = 117.
caD easily sxplaiD, that the n€xt inerr gas, if discovered, will have # 7p6 as its outer
(iv) Itr a similar way, we
electronic confisuratioD and its atomic number will be (l l2 + 6) = f 18.
Q. 5. What rrE super he{vy eleDents ?
Ars Elements with Z > 100 whici have high densities are callcd super hearT elements.
Q. 6. W'hat would be IUPAC rlame6 sDd syEbols lor elemelts vith otoDic truDber8 12a l?7r,.;l,ql4g andli0?
Ans. Ftom the Dble 4.5, the roots lot 2, 7 , 5 , 9 and 0 are bi, sepl pent, eru and ,n? respectivcty. Therefore, their
naDcs and symbols are :
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4144 Pradeep's
z Nome Syurbol
Urbibium trbb
127 Unbiseptium Ubs
735 Untripentium UtP
149 Unquadennium uqc
150 Unpetnilium upD
Q 7. Arrange the follo*irg elements
(i) in the increaslng order of metallic chrracter : Si, Be, Mg' Na, P (NC.E.R.T. )
(r'i) in thc incr€asing order oftron-metallic charncter : B, C, Si' N, [, (N.C.E-R.T)
Ahs. (i) ArrangiDg the elements into differeDt grouF and periods in order oftheir increasing atomic nuDlbers, we have,
1 213 14 15
Be
Na Mg Si P
We know that the mstallic character increases dot n a Sroup and decrerses along a period as we mo!r'e fron'l
left to rigbt. Therefore, Na is the most metallic element, followed by Mg and Si, while P is the least metallic
element. Among Be and Mg, Mg is more metallic thaD Be. Tberefore, the overall increasing order oimetallic
aharacter is P < Si < Be < Mg < Na.
(ii) Aranglng the elements into different groups and periods in order of their increasing a tomic numbers, we have,
13 14 15 16 1',7
BCN-F
si- R
EE
Sitrc€ the metallic charactcr iDcreases do\rn the group aDd noD-metallic character increases along a period
from left to right, therefore, Si h the mct metallic or the least non-mctallic element. The ovcrall i[creasing
AR
e. E. The elGmcnt 119 hss not been discovered. Wh6t could be the IUPAC nome ard symbol for tlris elemelt ?
On the basis of ihe periodic trble, predict the clectronic configurstion of t}is eleme[t and also thc formula
S
N
Ans. (i) The roots fot l andg arcun a ) erw resp€ctively. Therefore, the name for the eleolent with Z = 119 is un
IIT
Q.9. Why has the zcro group been placed at th€ extreme rlght ofthe perlodtc aable ?
Ans. Thisin ac{ordance with their electronic configurations because each Period starts with the fillig of i-subshell
is
and is completo after the filling ofp-subshell of the saDrc principal shell.
e. 10, Wblch ofthe elemcnts Na, Mg, St and P woulal hsve the grcatest dilference betwcel the lirst ond
the seco[d
- ionlzatiou enthalplc+ Brielly explaln your anatier' <N'C'E'R T-)
Ans. ADong Na, Mg, Si aDd P, Na is ao alkali metal. It has only oDe electroo in the valence sbell, therefore, its IEt
is very low. However, after removal of one electron, it acquircs neon 8as configuratioD, l e,
Na+ 1ts2 *2lpt. Therefore, ils Iq is expected to be very high. consequenrly, the difference in first and
seco[d ionization enthalpies would be Sreatest is ca,se ofNa
Howcver, it may be noted here that in case of Mg, si and P, although their IEI will be much bigher than that
ofNa but their IE will be much lower tban that ofNa. As a result, the difference in their respective IE1 alld
Iq would be much lower than that ofNa.
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CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PHOPEBTIES
4145
Q ll Tlle lirst iohization enthnlPy ofmagnesirm is higher than that ofsodirlm. or
the other haDd, the sccotrd
iorizntion enthalpy ofsodium is much higher th; that ofmagnesium. Explain
Ans The first electroD in both the cises tlas to be remor'ed ftom the 2f
iN:C.;-i.f)
orbital but nuclear charge ofNa is less than
tioD of Na + is lp zrz 2p6 , Le ., that of Doble
isvery difficult. ln case of Mg, after the loss
tbe second electror. is to be remc,vcd from
(r) rhe sizcs of a,ions arc usuafly biggcr than those of the cations, !'. a, the sizes of sz -, cr- and Br - ions are
bigger rhaD those ol Bcz+, Mg2+ anri Na+ ions.
(ii) Witlrxr a group, thc iooic sjze increases from top to bollom
,tbercforc,ionic $ize of Mg!+ ion
R ir bigger tlon
tltot of Be2 r . Likc$,i\e, ioni(. size of Br- i.r bilger than tltat of
Cl- ion.
EE
(iii) AnoDg isocrectronic roos, higher
the +ve charge, smaller rs rhe size. Thus, rbarc rize ofNa+
AR
b biger thon
lm of M{+ Furthcr, anroDg isoereclronic ioDs, higher the
-ve chargc, bigger is the size. Thus, rbntc rize o/
C
Furthcr' thc incrcasc ln ionic sizc (luc to addition ol onc nrore shell
N
alr the above vie\rs, the ionic size of aI the risted ions increascs in the order :
Be2+ < u/+ < Nat < cl- < s2- < Rr- _
(;roup 13 14
2nd period B C
3rd period At Si
(o) since IEf iDcrcases arong a pedod but decreascs down grou
a p,Thereforc c htl, the highe
entlnlsty.
frfrt ionization
(r) Since electron gain eDrhalpres be(.omc more negarrye ak)ng a priod and less negativc down a group,
thctefore, C ho.\ thc mott negative electron gain entloipy.
(c) siDceatomic radiidecrease arong a pen*r bur incrcase down a gro rp,
therctorc,Ar rw he raryesl alomic rudhlt.
(d) since meollic characrer dccrc.rses arong a pcflod. but
iDcreases down a gfoup, th ercforc,Ar ho! rhe moNt
netollic charocter.
2nd poriod N O
3rd Period P s
(a) Since IEl decreases down a grouP, therefore' I
since N has more stable
difficult rc knock out an
has exactly half-filled ele
enthalPy of these clemeDts follo$'s the order :
Thus, the werall increasing order of first iooization
s<P<O<,.V
similarly,Nhase)(acttyhalf-filledetectronicconfigurationinthe?-subshellbutohashiEhernuclearchar8e'
to such an extenl' thai electJon gain enthalpy of N is
But thc addition of an efectron to'X causas repisions
alualty positive white that of o as sxPccted is Dega ivc'
R enthalry of these eloments follou/s the order :
Combidug to abwe r€sulls tie incf,easiDg order of ne8ative Sain
EE
N<P<O<S.
alons a oeriod' therefore' O is the mGst
(c) Since tron-metallic character dert€ases down a SrouP but increases
AR
Accordinr
funoion oi n.,, *.,Sf,o.
S
Q. 11. what wourtr rre the IUpAc Dame atrd syrnbor for the
eremelt with atohic rumber r20 ?
Ans. Unbinilium, Ubn
Q' 12 Which one amonE the fororving elemchls_has the
rowesr
- first ionisation entharpy and whicrr one hns the
highest lirst ionisntion enthalpy ? Li, K, Ca,
S and Kr.
K has the lowest lonlsntion enthalpy and I(r has
the highest ionisation enthalpy,
Q. lJ.
H[1"#t;,:it":",ii[il:;J* n'"' in separate rows at the bottom oi'tr,. p""ioai"
,nbre. Exprain rhe
Ans. These have been praced seDararelv at
the bottom of the periodic table for conveniencc.
rhc body ot lhe periodrc rabte. rheieriodrc rf they are placed in
,uor. *iri t.oir.Iilr.n#iy iln!"unu
Q. 14. Givc four exsmples ofspecies rvhich are isoelectronic "rro.^orr..
with Ca2+.
Ans. Ar, Kr, Cl-, 52- or p3- are isoelectronic
with Ca2+
Q. 1s.
:"T":f:H-"1;l;.'ir1'ilil'".;J,Yrlffi,l:tomi.veisht = 3e'e) has heen righrrv praced beforc potassium
Ans. This rs beouse argoo (Z
= 1g) has lower atomic number than potassiunr (Z = l9).
Q. 16. Which has a larger.adius ? (i) MgorCa (ii)SorCI-
Ans. (i) Ca (i,) S.
Q. 17. In terms ofelectronic configuration, what
the elements ofa giver period snd
ADs. o group hqve in commor ?
r.;
'i"J;J:ffiil:J:f.r&n# H:liiii;:'li*:i"q,ur""d
Q. It. Whict two elements ofthe followitrg beloog
";.;;;;,"n-"1,oup,,," n,,oerore,ec,rcns in
?
wlrich are inner trnnsition elemenLs
Q. 21. Which rmorlg the following ere transition anil
58, Blq Er' fm' Fe' Pb' Cr, Co' Ar' Zr'
Ce
stion
I
Sec.4.1. 1. What was the Deed for classlflcation of elements
to 4.6.
justificailon'
2. Define Modern Periodia law Give its theoretical ? Explain with two exaolples
3. What is the cause of periodicity in properties of the elements
following elements
4. Predict the deDsity of Cs from the densrty of the
( 0 86 9cm3 Ca 1.548 g/cm3
.532 glcm3
Sc 2 gg1 llcrll3 Rb 1
enthatpy Oepends.
,,
S
24. Explain why ioniarion e own a group of rhe periodic tabte ? 'il.t:;X?,
IIT
25. The first live successive i ofboronatonrare aOO, 2427, 3658, 25OU antJ32g24
kI mol-l. Explain these res.
26. Explain rhc Iollowing :
(i) IonrzatioD eDthalpy of Mg
more than rhat of Na and Al.
is
(ii) Ionizarion enthalpy ofDrtrogen
is more than that ofoxygen.
27. Why is rhe ionizahoo enrhalpy of Be ntorc than that of B ?
Lphin.
2t' If we coDsider ionizarion entharpies of erements in lhe second period
from Li ro Ne, rhev ordinarik
increase but Be and N have rrigher ionizat;;
endi;;;;;.'
them. Why is lt so ?
sre J.15. 29, Explain the term electron gain enthalpy ? How does it lEry
"il o;;$;;;J;il;iih":;,#"iJ
along a group and across a period.
30, Explain the terms jonization enthalpy and electron gain
e;thatpy ?
ean by successive electron
" Sain eoth;lpies? why is rhe second erectron eDtharpy ofan
"'r'i,itJoo..ffi:f
32. Flalogens have very high ncgative electroD gain
enrhalpies. ExplaiD.
33. Electron gain enthalpy oflluorinj
is less negative thanthat oichlorine.
Explain.
34, ble dases in positive. Explain.
35. , srate which atom/ion has higher ionization
entbalpy and more ncgative
47. Fot the main group of the periodic table' the metallic
,
IIT
Src.l.lJ
1,, J.l ti
,4*
p-B,tTrt,ONA I- IUSE F UTL'IN:FO, lMAllilON
R
EE
d.
AR
C
S
N
IA
l€6.
IIT
1ls2
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CLASSIFICATION OF ELEMENTS AND PERIODICIry
IN PROPERTIES
4ls3
c&s.r. -P.ll.T.
Q. ?, The tirst iotrization eDergy of carbou atom ls
Q. l. ArrEtrge tbe elcEeDte ofs€roDd
lroriod ltr older
greater than that of boroh whcr€ss the reycrse
of ircrrasing s€coril ionizatiou enthalpies. is true for the second iorization energy ExplalD.
Ans. The electronic configuration ofthe ions obt2iDed (u.T 1989)
after removal offirst electron ftom the elements
(ii) Shoc iD B+, thc ele(troD Q.3. ArraDSg the foltowilg ious h order of ttreir
has to b€ Emoved
ftom a more stable tully filled 2 ,{rbilal while in bcEositrg iodc ndii I
Be+, it has to be lost from the less stable balf_
fillcd 2r.orbital and furthcrmore, tbe lcs of an R
AEs,
EE
more stable Be2* ioo
AR
on, theteforc, IE oI Be
2
y)^l!!: ant yz
C
?-,:
:b, ioDs and
are soetectrodc
?p6) a3+ 6i
2oe1
-hai
S
(iri) SiDoe less ellerry is requircd to remove an.r_ each one of these
N
clectrooic configuration is :
i4UETT UES.Tr,0,
7. R
Which of the follov/iDg combinatioDs contains
ooly
EE
of
1-
" ln loDffrom ofthe periodictablc the properties isoelectronicsPecies I
iii" ,r" , periodic funcli()n of lheir
AR
"Lh"nt. (b) bnizntion enerry (4) N3-, O2-, cl-, Ne (b) F- Ar ' S2- , cl-
(d) atomic size '
C
in the
2. Total number ot vertical columns (grouPs)
N
loDg
(a) 8 (D) 18
IIT
(c) lt ('/) 16
3rd period is
3. Number of elemcnts Present iD thr'
(a) 6 (b)32
tiofl ofenergY ?
(c) 18 (d) 8'
e- - Cl- (D)o- t c- - 02-
4. The number of periocls in thc Pcriodic table (.r) Cl +
is
It. Which among the following species has the same @)G*zpcaP 3pa3a1 4z
N
peDultimate shell
(b) 1s2 ztz 2pG rt2 3p6 3dto 4$z 4ps
?
IIT
(At' of
31. The electronic configuration of Gadolinium 39. The radii of E F-, o and 02- are in the order
No. 64) is
(o)02-, F- > F> o (b)F- > C)2- > F> O
(4) txol4f s/6f (b)
(c)02- > o > F- > F (d)02- >F- > o > F'
(c) [xe]4P sd5 tu2 (d)
tssn
40. Which of the folloMDg has maximum ionization
T]ne incorrect statement among the following
!s
32. - potential ?
ra) Tbe first iotrizaiion poiential of Al is less than
(a) Be (b) K
the first ionization potentialof Mg' R (d) Ms
(c) Na
EE
/b l The second ionization poieniialof Mg is Sreater t.l.!-l.M.S. l9e9 \
' ' ihao ttre second ionizaiion Poteniull of Na'
AR
(I-I.T 19en
IIT
37. a
b 29. b 30., 31. , 3Lb 33.b 34, b
2A.
40, c 41, s 42. c 13. b
3E, a 39. d
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CLASSIFICATION OF ELEMENTS AND PEBIODICITY IN PROPERTIES 4ls7
(c) Wbaker electron-electron repulsion in Cl
(c)I+>I->I (d)I->I>I+
(d) more r?cantp-sub6hell in CI. t\D.C.l;. 199s.1
\.c.R.s.8. t!]t.T 19e7 lt|.p. (..L.t:.2at)0)
45. Among the following groupings, which represents 54. The ionic radii of N3-, O2-, F- and Na+ fo ow
the collection ofisoelectronic species ?
the order :
(a) No+, C;-, cot, co
(o) N3- , 02- > F- > Na+
(6) N2, q-, co, No
(b) N3- , Na+ > Ctz .l'
(c) CO, NO+, cN-, C;- (c) Na+ > 02- > N3- > F-
(d) NO, CN-, N2, Ot.
,(.Lt \ t::. ey.l: 2ot)/j) (d)C2-rF->Na+>N3-.
45. Electronic configuration of most electronegarive (,t7. I P :,1.'t: ! 9e tl, 2 0 00 )
element is 55. The first ioniatioD ener$/ of Na, Mg, A.land Si are
in the order
(o) 7 sz zsz zp6 3 s1 (b)tiz]zp63i3ps
(a)Na < M8 > Al < Si (b) Na > Mg > At < Si
(c) 1$2 2 12 2p5 (d) 1 s2 2 s2 2 p6 3 s2 3 p6 .
(c)Na> Mg>Al >Si (d)Na<Mg<At<Si.
LtI:;. B.H.U. 20A0t
47. The bond lengrh in LiFwillbe fiI.PPAr.r 20t)0\
56. What is the maximum number of electrons which
(4) Le&s than rhat of NaF
can be accommodated in an atom io which the
(b) Equal to thar ofKF highesi principal quantum number is 4 ?
(c) More thar thar of KF (?) lo (D) 18
(d) Equal to that ofNaE jC p.tll:200t)) (c)36 (d) 54. t1 1,1,11 1 1,1,1t1
4E. The correct seque[ce ofatomic radiiis R
57. The frst ionization energy for Li is 5.4 eV and
EE
(a)Na > Mg > AI > Si (r)At > Si>Na>Mg electroD affinity of Cl is 3.61 eV The AH (in
(c)Sr>Al >Mg>Na (d)Si> Al>Na>Mg. kJlmol) for the reaction,
AR
49. The first ionization eners/ will be maximum for iftbe resulting ions do not combinewith each other
S
is1tcv-16xlo-leJ)
N
61. The set representing ihe correct order of first (4) caz+, cs+, Br (b) Na+, Ca2+, Mg2+
ionization Potential is (c) N3-, F-, Na+ (d) Be, Al3+, cl-
(b)Be > Mg > (l.l li.li.li. )'4)-l
(a)K> N,r > Li Ca
(c) B > C > N (d) Ge 70. 'l}lc rons o2-, F-, Na.l-, M82r 'ncl 'N3+ are
"' i,|,. .rr, , isoalectronlc. Their lonic radii show
among (a) l stgnilicant increase from 02- lo Al3+
62. The correct order of Ist ionization potential
following elements Be, B, C, N, O is 16) a signilicant decrease fronr
02- to Al3+
(a)B<Be<C<O<N (c) an increase from 02- to F- and then decrease
(c)Al<M8<s<P (d) M P (a)Mg < Si < Al < P (6)P > Al > Mg > Si
C
65. Eka-aluminium
IA
(a) Gallium and Scrmanium 74. The highly metalliceleorent willhave the configura-
IIT
tion of
(o)2,8,7 (r) 2, 8, 8, 5
(c) 2, 8, 8, 1 (d)2,8,2
orygen atom.
(a)ItnlTP 7p6 (b) Itnl7s2 5f 1 6dto
EO. Which-one of the follol ng sers otions represents ho
C
thc mllection ofisoelectronic species ? (c) Url 6i2 fl4 5d10 6p6 (.r) None of these
S
N
i1 ii".i-i-::,. i:.:.
ole Choice Q.uesLions
6. In heavier elements, HuDd,s rule is not alwa)6 fol-
I5. Front z-= l2l s.138, rhe filtiog up of g.
lowed. orbitals
oe€tns Iorr\hrch lhcre is no provision in
t. Since lhe size of K is larger than K+ fl .34 A) and set-up of thc prriodic table.
he pres€nr
rhar of F is smalter than rhar of F- (l.t A), 17. Bigger rhe size, sma er rhc LE.
therefore, optioD (o) is conect.
9. The second electron aflinity of an element is nega- l& Ca2+ = 2,8, S.
trve, re, energy is absorbed. 22. B:th (h) irrr(l (l) have simitar fiacily half.filled
11. For ratio of anion size to catioD size to be lowest, elc(tronr r,.ntiSUratron, bul rhe slzi of
snlaller lhal rhirt of (d, 1af is
anion should be smallest (F-)
and catioo ro be
biggest (cs+), rd , option (d) is correct.
14. IE abruprty increases (ria IEo > > > I%) wben
an
electron is knocked out from the noble gas
core.
77. a 7t. c i9. c t0. a al, b ll2. a 3.!. r E4. a E5. c t6. c
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Ncr4 CouYse Chemistt4'
4l60
29. IEz of O is higher than that of F because in case of 46. F O sa 2 t2 2 Ps ) is I hc n]ost electroDegativc clenlen t-
(). the second clectron has lo he renloved from fl 47. Due lo smaller size ol Li tban Na ot K, LiF has
more stable completely hrlf-filled electronic con- smaller bond leogth than NaF and KE
frguration,ia, O+ 1t s2 2s2 2Ptr}ptyzPbwnnein 4E, In a period, atomic radii decrease from Ieft to rigbt'
Beiog smallest, hrdrogen has thc maximum IE1'
case of E this is lrot so, ie- F+ 49,
(1 !7 2? 2p?,2 Ply? lt.\
r
"ite^d removal o[ 50. Inert gascs have zero clectron-affinity'
a[other electron from F+ giles a rnore stablc s1, Both Na+ and Ne have 10 electroos each-
conrptetely half filled electrooic cortfiSuration' ' a' p6' 36'
s6. I s2 2 rz 2 p6 3 sz 3 p6 3 4to 4 57 4
rt+ 0 ,2 2s2 2 P:Z Ptyz plr).
57. AH =(s.4 -3 6r) x (1 6 x lo-leJ)
--' Energy is released t hen an electron is added
30. to O
x (6 023 x roz3;x10-3 = 1?2 5 kJ rnol-1
Urt has to be spent when an electron is
"ln"tg, ftom top to httom'
added to o-, F- and Na+' 61. Witbin a grouP IEt decrease6
J1. The tilling of4 f-shellbegins onlywhen one elcctron 62. Because of sxtra sEbility of exacily half-filled
has alreaiy been added to 5 d-orhital' electroflic conf,Euration ofN, its IEr h higher than
32. lEz of Na in case
thnt of O. Furthet because of higher nuclear
ofNa, the d fronl charge, tE1 of C is higher thao that of Be and B'
(wal of
the noble Amongst Be and B, tbe IEr ofBe is hiSher than that
second electron gives a nobe gas corc' ot Be a 2 J-clectron is to
of
33. Be has higher IE, than B. re of B a 2P-electroD is to be
i. order is (a) ie , B < Be
Bi8ger the sizc of ions, larger is lhe distance
be-
]4. R
<c<c)<N. "ralt
EE
t\I'eeo the ccntres of their nuclel'
elgctrons 63. As th€ Dumber of shells iocreases, atomic radius
3t, Each SrouP has a fDGd number of valence
AR
accordiIlgly.
39. The size ofOz- > F--and lhat ofo > E Therefore' incl ea.ses
Oz- > F- > o > F 64. Because of extra stability of exactly hau-filled
C
tion Poterltial.
IA
41. Anrongst lqcroa, GF3, Cro2 and CrCl3, Cr has of Al because in case of Mg, electroo is to be
IIT
ADDITIONAL ITfrSTT.
TruelFalse Statemente
C
An elenent with atontic number 47 is a transition 5. SecoDd electron affiDity is always negative.
S
The second period contaios 8 and the third period periodic table-
IA
contains l8 elen]eots. 7. The size of CI- ion is smaler (han that ofs2- ion.
IIT
1 The size decreases as Cu > Cu+ > Cu2+. t. The decreasiDg order of electron affioity of E Cl,
4. The Iirst ionization ener$/ of N is lower than that BrisF>Cl>Br.
of oxyge[.
(I.I.I 199i)
Fill ln The Dlanks
1. Ar, elementwith atomic nunrber 35 belongs ro..... t. valency of ap-block elen]ent is equal to eight.....
block. rhe nuntber ofetectrons prescot inthe -.... s[ell.
2. Each series ofd-block contains ..... elemeob. 9. Wben an elcclron is added to a uninegative ion,
3. The lirst ionization enersr of N is ..-.. than rhat of eDerry s ..... .
O while thesecond ionization eDer$/ of..... is higher 10. AD clementwhich lies right abde and belc, Cd in
than that of ..... the preiodic table are .... and .... respectively.
4. The radii of Fe, Fe3+ and Fe2+ decrea-se iD the 11. On thc Pauling electronegativity scate, the element
order. .... next to F is .... . (Roorkee 19E9)
5. In the second p€riod, the most €lectroDegative and 12. Caz+ ion has a smaller radius that K+ because it
electropositive elements are........ and ...... respec- has (I.r.T. t9e3)
tively. 13. The radioactive series consisting of man-made ele-
6. The general outer 6hell electronic cooliguration of ments is called ..... elsments.
/-block elements is .... . (A.I.S.B. 1996)
7. Among the isoelectroDlc ioos, the ionic size io- 14. The clectrooic configuration of atoms and
creases as the ..... charge on the ion .... . ...........provide a basis foi periodic classification.
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4162
Pradeep's
1. (a\ z. (a) 3. G) a. (e) s. (b) 6. (a) 7. (c) E. (c) r. (D) ro. (c)'
THUE,/FALSE STATEMENTS
l.Ttue2.False,bothcontain8olenrents,3.Ttue4.Fhlse,firstionizationenerslofNishiSherthao
that of O 5. Ttue 5. ltue 7. Ttue E False, Cl > F > Br.
FILL IN THE BLANKS
1.p- 2. ten 3. hiSher, oxySer, nitrogen, 4. Fe > Fe2+ > Fe3+ 5. Fluorine and lithiu m 6' 1n - ) f-ra
l0' zinc, meroury 11' qxygeo
6-y
|
a0- n?.7. negative, iocreases E. minus, valence 9. absorbed
i2. higher ouclear charge 13. transuranic 14. aufbau principle'
R
EE
, MATCHING TYPE OUESTIONS
AR
HINTS/EXPLANATION9 to
N
IA
IIT
R
Er halpy changes in chemicar reactions-srandard entharpy o, tormation, Hess,s raw
of consrant
EE
heat. sumrnaiion, bond enthalpy, rneasurement ol enrhalili of re"citon",.n"rgy;t";;;;;ii.;
teactions-
AR
SEC'TION I
N
IA
5/r
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512
ing the systent is called surroundings. Animals and plants are open systems fiom the
thermodynamic point of view.
C
SURROUNDINGS
OPEN SYSTEM
SURROUNDINGS
CLOSED SYSTEM
TEA IN
THERMOS FLASK
o ISOLATED SYSTEM
INSULATION
siv€ ProPerti€s).4 (,
Isothcntral process. lVhen a process is
of chemical sPecies caried out in such a ma\tter thot the temperature
is called s macro' remains constanl throu?hout the process, it is cqlled
n such a
tem tothe
keep the
temperature of the systom cofftant.
ature, Pres- (ii) Adlabatic process.When a process is car'
oiling point ied out in such a manner thqt no hedt can tlow from
es or ther- lhe system to the sunoundings or vice vena i'e' the
modynamic properties. These are further classified system is comPletely insalated from the sttround'
into two types as follows : ings, it is called an adiabatic process.
(iii) Isochoric process.It is a Process duing
which the volume ol the system is kePt constant '
(iv) Isobaric process. It is a process duritg
R
which the pressure ol lhe system is kePl constont'
EE
?. Reversible and Irreversible Processes' The
AR
:
N
(ii) InteEsivc properties. These are those imagine a gas confrned wi&in a cylinder provided
IIT
PILE OF
SAND
PISTON
EXTERML
It is of interest to note that aD extensive PRESSURE
practice.
S
SECTION II
ZI'ROTH LAIY OF THERMODY\ATIICS
5.3. Definition ol Zercth Law ,' , "" - ' --::.'
_. As mentioDed iu the beginning of this unir,
this lawwas put forward much a_fter thi enunciation
o
FIGURE 5.6. (a) Thermalpquilihrium I.(tweLn
bo,lies A anrl c
(b)-Thcrmal equilil'riun between hodi.s B an,l C
(c) lhermal .,quilibrium between hodi.s A and B.
v2
If
the extcrnal prcssure P against which the
gas expands remains almost constant throughoxt Hence ,=- [l'iru
,rRT
ihc process (so thatitis ineversible apansion), tho )
above result may be written as R v1
EE
v2 For isothermal expansion, T = consta so that
AR
( v?
w=P I dV = P (vz - V' ) = P. av Ir
C
J
vl )
N
v1
IA
volume of the gas (or the system). This is thq = - nRTln ;;Yl
cxpressioa for work of irreversible expansion.
If the external pressure (P) is slightly morc
than the pressure of thc gas, the gas will contract = - Z.:03 nRT log 3
i.e., the work will be done by the surroundings on
the syste rn, However, the same formula will apply = - 2.303 nRI log I
Pz
for the work done.
It may be mentione rJhere thatP is lhe extemol
(At const. temp., P,,r, = ,rr,
prcssure and hence is sometimes written as Prrr so ". f, = | )
that r? = P.rr x AV
The -ve sign indicates work of expansion.
Sign ofw. Accordinglo the lutest S.I- convetr (3) Heat. Just as work is a form of energy
lion, w is takerl as negtive i[ work is done by the which is exchanged between the systern and the
.ry.irem whereas it is taken as pasrlive if work ts done
on lhc slstem. Thus [or expansion, we wrilc
w = -P AV
and for contraction, we have
w = PAV churyed between the system and the surroundings as
a fesult of tlv differcnce oI temPefature between oI some olherform oI met&) nust be produced. Fot
,lrem. It is usually represented by the lctter 'g'. example,
It maybe pointed olut ahat both heql and io* (o) In the operatioo of an electric fan, the
oppear onty at the bound.ary of the system. electrical energ5r which is consumed is converted
Sign of'q'. When heat is given by tJte system iato mechanical work which moves the blades.
to the surroundiDgs, it is given a negntlvc sign. (D) The electrical energ5r supplied to a heater
When heat is absorbed by the system from the is converted hto heat whereas electrical energy
surroundings, it is given a posttive sign. passing through the frlaraent of a bulb is converted
Units of 'q'. Heat is usually measured in terms into light.
of 'calories'.1 calorie is d6ned as the ryontity ol (c) Water can bc decomposed by an electric
heat required to rsise the tempemturc oI one gram of
currsnt into gaseous hydrogen and orygen. It is
water thrcugh ]"C (in the vicinity of I 5Y) .
formd that 286'2 kI of electrical energ5r is used to
In the S.I. slEtem, heat is expresscd in terms decompose 1 mole of water.
ofjoules. The two types of units are related to each
other as under : H2o(I) + 46. 2 w H, (c) + o, @)
: ---- +
I caloie 4' 184 ioules Eectricel
cncra/
which means the same thing as
This energy must have been stored in
1 joule = 0.2j90 calories
h/drogen aod orygen since same amount of energy
It may be noted that whereas internal energy ia the form of heat is released when 1 mole of water
is a state function, work and heat are not state (liquid) is obtained ftom gasoous hydrogen and
functions because their values do not dcpend mere- orygen.R
ly on the initial and final states but depend upon
EE
the path followed. I
Hz@) + H2o(t) + 2K' 2 W
AR
moving faster with greater randomness in different Thus 286' 2 kJ of electrical energy which was
S
directions. However, when work is done on the supplied to the slnten (rub*ance under obseNa-
N
+q
(HEAT (woRK
ABSOREEO) DONE ON THE
SYSTEM)
(i) By supplying heat to the system conditions of temperature, Pressure and volume is
E^ (state A). Now suppose the conditions are
(li) By doing work on the system.
rhanged so that the internal energy is EB (state B)
Suppose the initial internal energy of the sys-
: (Fie. 5.9). Then if internal energy is a state functioo'
tem Er be
ih"-difl"r"nc" AE = Es - EA must same
If it absorbs heat 4, its internal energy will
become: Er *g
If further work w is done on the system, the
internal enerev will further increase and become =
-Let
E1 + q + w. us call this final internal energy as
E.Then Ez=Er+q+w R
EE
or E2-Et=q+w
AR
E
Tlvo interesting results follow from th€ math-
ematical formulation of the hrst law of ther-
EodlDamics, as under : - VoLUME
-+
(i) Neither 4 nor w is a state function, yet.the FIGURE 5 9. Changes in internal
qunatiiy q +w ( = 69; is a state function (be- energY in direct andieverse Paths'
causc AE is a state functioa).
(rl) For an ideal gas undergoiag an isothermal Internal energr change ln terms of heat
Herce q= evolved or absorbed. From hrst law of ther-
change, AE = 0. -w modynamics, 4=AE+PAV
i.e. the heat absorbcd by the system is equal to
Ifthe process is carried out at constant volume
work donc by the slstem. AV = 0. The above equa-
(say in a closed vessel),
Itrternal enrcSr 18 I ststc furcdotr - A deduc' tion tben reduces to the form
don from the Flrsiiaw of Ttermodynamlcs. Sup-
pose tie internal cnergy of a system utrder some
dE = q, @ irdicating constant volume)
;oi using thc symbot U in placc of E fot intcmal cncrB/, wc c8n \vrite
AU={+$,ond4-AU+PAV
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FIRST LAW OF THERN,IOOYNAMICS AND CHEMICAL ENERGETICS s/1'l
tt
PP
like internal energy, the work done during a
V+ V+
process does not depend merely on the initial and
the final states of the system but it depends upon
the oath followed. Hence work is not a state
funciion but a patb function. This may be made
clear as follows :
= -107325 x 4 x 10-3
J J= -405.3 m ot 27oC. Due to sudden leakage
C
The negative sign implies that thework is done through the lrcle, all the gos escaped into the etmor'-
phere and the cylindcr got empty. If the atmospluic
S
by the system.
N
by the gas.
AU = q + w = 0 _ zl05.3J
IIT
PRAbLEMS FOR
1. 500 joule of heat was supplied to a system at con- even when 2In joules of hcat is supplied to it ?
stantvolume. It resulted in the increaseof tempera-
ture ofthesystem from 20'C to 25'C. What is the
[415- rk dono by tho sltstcm = 300.1]
3. Calculate thc work done when 1 0 mol of water at
.
cha[ge in interDal eners/ of the system?
373 K!"porizes aSainst an atmcpheric pressure of
l'rr'" aE = 500 JI 1.0 atmosphere. Assume ideal gas behaviour.
2. What would be the work done on^,y the slstem if
[415.31fi1J]
the i[ternaleDerry of the s]stem falls by 100joules
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FIRST LAW OF THEBMODYNAMICS AND CHEMICAL ENERGETICS s/13
LI
l At constant volurre, Av = 0. Applylng _ 1x0 08?1 x 373 _
30.6 L
LB = q + w = I + PAYwegetAE = I = 500 J.
3. pv=rRrorv=n$ "-,:t":,,ff"jiT;.J;,:,rf :"J"r..,',
5.7. Enthalpy or Heat Conteni Thus if H, is the enthalpy of the system in the
If a process is carried out at con^stant pressure final state and H, is thevalue in the initialstate, then
(as is usually the case, because most of t he reactions Hr=Er+PV,
are studied in vessels open to the atmosphere or if
a system consists of a gas confined in a cylinder iind Hr = E1 + PVr
frtted with a piston, the external pressure acting on Putting these values in equation (vi), we get
the piston is the atmospheric pressure), the work of qp: Hz- Hl
exparsion is given by
ry= - PAV ...(r) ...(vii)
where AV is the increase in volume aad P i.s the where AH : Hz - Hr is the enthalpy change of the
constant pressure.
system.
Acording to frst law of thermodynamics, we
know that Hence enthalpy changc of a sysbm is eqsl to the
R
hcst absorbed or evolvcd b! the qstcm at corlttant
EE
q=LE-w ..,(ii)
Prslflfe.
AR
is the work done by the system. reactions are carded out at constant pressure (i.e.
S
qP'vte get
(vii) in equation (ur), we get
qP:AE+PAV -(r:rr)
AH = AE+PAV ...(viii)
Suppose when the system absorbs qrjoules of
heat, its internal energy increases from E, to E, and Hene tle entlwlpy change acconryarying a proes
the volume increases from V, to Vr. Then we have
AE=Ez-Er -.(iv)
and AV=Vz-Vr ...(v) Physical concept of€nthslpy or heat content
Putting thesevalues ia equation (rri) above, we In the above discussion, the enthalpy has been
get dehned by the mathematical expression,
qp=(E,-El)+P(V2-Vl) H=E+PV Let us try to understand what this
quantity really is.
o, Qt : (E; + PVr) - (Er + PVr) ...(vi) It has been described earlier that every sub-
Now as E, P and V are the functiors of state, stance or system has some dehnite energystored in
therefore the quantity E + PV must also be a state it, called the internal energy. This energy may be
function. Tfte thermodynumic quantity E + PV is of many kinds.
called the heat contc[t or ent}ldpy oI lhe system The merg slored within the substance or the systen
andis represented bythe symbol Hi.u. the enthalpy that is avaibblc for conyers n into htat
h4at is calted
calte.l
may be defined mathematically by the equation the h.sl con ent or enthalpy o! the subsmncc or the
qdlem.
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5114
As H = E + PV and absolute value of E ses, we are concerned only with the changes in
cannot be determined, therefore, the absolute enthalpy (AH) which can be easily measured ex-
value ofthe heat cotrtent or enthalpy ofa substance perimentally. Further, it may be mentioned here
or a system cannot be measured. FortuDately, this that as E and V are extensive properties, therefore
is not required also. In the thermodynamic proces- the enthalpy is also an eatensive propefiy.
l. Both intemal enerry and en(halPy are state furlc- 4. IDternal enerry change is tbe heat svolvcd or ab-
tions. sorbed at constantvolume while enthalPy change is
2. Both are exteDsive ProPerties. that at constant Pressure ie. AE = qu , AH = 4p.
3. The absolute t?lue of nei*lcr inEmal eDerry nor 5. In a cyclic process ie. when the q6tem returns to
enthalpy can be determined. origi[al state after a number of changes, AE or
AH=0.
-.(rir)
AH=AE+PAV ...(r0
C
or aH =AU +d,,rRT
Here L E= (D-\\
_ t 8os.ou,
-
In this reaction, O, is the only gaseous reac- AH (or qr) : AE + d,r8 I{T
C
=-3263.e. ,rrr
N
Nts=nP-fi' \ 2/ ( 1000
IA
'"
=- 3263.9 - 3.7
IIT
:(t-, _1 :
+ : - 3/2
l-= -3267 6 kJ mol-r.
2 -
1, The heat of comhustion of CHa k) ar coDslaDl atmcpheric pressure and 373 K is ---223.6 kJ
volume is measured in a bomb calorimeter at 29g.2 mol-l of NH. NOr(s) decomposed. What is the
K and found to be J/mol. Find rhe value
-885389
of enthalpy change. value of AU for the re€ction under the same condi-
,rns. _t90347
[ J mol -l ]
2, The enthalpy change (AH) for rhe reaction
tioDs ? (Civen R = 8.31 JK-l mol-l)
N2G) + 3H2G:)- 2NH3@) is (A.1.5-B- 1998) [ Ans. .9 mot -l I
-232 kI
,
38 kJ a r 298
K. Whar is AU ar 298K ?
-92 5. When 0.532 g of beDzene (c6H6), boiling point
(A.LS.B. 1991 S, 2@1, p5.8.95, N.C.E.P-T.) 353 K is bumt with exc€ss of uygcD in a coDstant
volume srstem, 22.3 kI of heat i! given out. Calcu-
I Ans . ___r7 . 42 kJ] late AH for the combustion process (R
3. The internal energy change (aE) for the reaction = 8.31
cHa6) r 2O2G) ...._ CO:G) f 2H2O (l) is IK-1 mot-l) (A.I.S.B. 199e)
During sdiabofc qpansion ofa realgas, enthalry (but trot intemal eners/) remaiDs constant. It is, therefore,
AR
ffi4. The iemperaturc at whici a real gas sho s Do cooling or heating effect on adiabatic expansion is called
C
Itrvelsior teDpcrrtuE Below this temperature i! shours cooling effect while above this temperaturc., it sho\^6
S
heating effecl
N
IA
tI2 and He have very lo$, inr€rsion tempc[atures- That is why they show hcating effect at rmm temperature
IIT
5.0. H.rat capacity, Specitic Heat c3f:ily Thus if dq is small amount of heat absorbed by a
and Molar Heat Capacity ,
!ii;i i: ::i: ,. , , :t: , ,':.:'.:.,,r'., r system whici iaises the temperature of the system
5.9.1. Delinitions. by a small amount dT (say from T to T + dT), then
the heat capacity of the system will be given by
Thc hcat capaciE of a ,\!stem is deJineil as the
amounl oJ heat requircd Ut rdire lhe tempersture oI c=# ...(,,)
the slslem througlt 1"C.
c- = =-s _- =
Tz - Tr AT
_-s- . (i),"u""ll;:'l:#J,tlf;*,ili':,11ili;"',t:H:n;l
Thus
However since the
temperature, therefore
considered over a very n
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FIRST LAW OF THEFMODYNAMICS AND CHEMICAL ENERGETICS
5117
\.4 .1 _ .rd.3
3x2"- J mol-t K-l ...(rr)
capacity. o[ water is 1 cal g-i K-l or Also, we know that the heat content or enthal-
N
IA
_
py of a system is given by
4 18 Jg-t 1-t.
H=E+PV
IIT
ts ls
.Fcranf.c.i.-,r<.it.a0bcsh^wn,hdltheint..,atencr./isindepcndentof\,olumcanddepcndsoilyonthe.Ercraturc
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Pradeep's
s/18
Alternatlwly, from equation (di), we can the system is to be raised through the same valuc as
directly say that at constant volume, then some extra heat is re-
(6q)" quired for doing the work of expansion Hence
"P_ dT
Cr, C,,.
=r?1 xCxAT
=10.0x045x(500-25)J
= 2137 .s J
(b)q=mxcxaT
2137'5=m x 0 13 x (500- 25)
or m :34 69
SECTION TV the energy required is greater than the energy
evolved, ifie nei result is the absorptiotr ol cnugt
ENERGYCHANCES and the process is called'endothermic' '
DURING CHEIVICAL REACTIONS Thus all chemicat reactions are usually ac-
5.1 o- General lntroductio n i:il:iiri:iiiii::r:
ges manifest and the use to which they are Put are
given below :
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FIRST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS
5/19
(i) Buming of coal ia air produces,hear. That surroundings is higher, the work is said to be done
is why it is used as a fuel o,l the system.
C (s) + O: G).-.* Co2 G) + heat. 5.1 1. Exolherrnic and Endothermic Reactions. .
(ii) Buming of naturalgcs (a mixture of lower
hydrocarbons) pro d\ces heot and lighr. Therefore, Exothermic R€acllo[. Thesg are tl]}[jy. reacrio$
it is also used as a fuel. which ue auatrqoudd br the efolutiafl o! hoat.
+ 2ozq)-
CHo (g) Coz @) + z}{2o(t) The quanriry of heat produced is shown
Methane + hear + light alongwith the products with i.plus,sign. A few
2qH6 G) +7 ozk).......,4co2@) + 6Hzo(t) examples of exothermic reactioni are givin below :
Ethane +heat + light C (r) + or(s) .._ Co2 k) + 393.5 U
(iii) Combustion of petrol (CroHrr) in at
automobile engine produccs /r eat and rvechqnicql
Hz Gr ,i
1
work.It is, thercfore, used as a fuel for automobile Nr6; + r-Hr1s) .........- 2NH3Q| + gz.4kt
engines.
cH4k) + zoz@)...-, Co2G)
2 CloHz2 (t) + 31 orG) ....-._ zo CO2 @)
+ 2H2()@) + 890.4 k.l
+ 22 HzoG)
11
.. - (i.v).Slow combustion of carboltydrutes
biological systems produccs,/rcar
in C4Hrok) + +OrG)........*
which maintains
the body temperature. ttor lsl +5H, o G) + 2658 kJ
CuH,rOu(s) +6 Or(g)......+ f agz@) +6lH2O (l) R
EE
+ heat
(v) Bumingofcandle rn ari produces heat and
AR
@)
IA
+ 16 H2O k)
IIT
HzG) +
1
zuJ
iorttl PRODUCTS
-Hzo0),
AH : -285'8 kJ mol-l PROGREES OF REACTION
Nzk) + 3HzG)- 2NHr(s),
LH : -92'4kJ mol-r
cHaG) + 2o2G)- Coz@) + zHzo(t),
AH: - 890'4kJmol-l o (L
J
c+Hro @ *+oz@)-4coz@) + sH2oG),
I
F
LH : mol-l zul
-2658 kJ
A reaction is endothermic i'e' heat is absorbed
PROGREES OF REACTION
in a reaction if the total heat content ofreactants is
less than that of the products, i'e', H* < H, R
EE
FIGURE S.11' (a) Exothermic rection
(b) Endothermic reaciton.
Then, according to the equation
AR
AH: Hp Hn,AHwillbePositive'Hence 5.1 2. Thermochemical Equation i::: ::::::::::i::::::: ::::i:: ::::i:i:::: li:::i: i:::::::i:::::i::: i :
-
C
indi-
S
is
cati the quanlilics of the differet reailants und
IA
Thus the endothermic reactions given earlier proittut^t'bul obto indicates lh'e &tttount of hectl
IIT
HzG) + Hzo(/)
C(s) + 2S(s).-..- CS2(/), irrrtd-
AH = +92'0kJmol-r + 285' 8 k.l mol-r
released when bonds are formed between the Lurnt. Hence enthalpy of combust ion oI methane is
N
If energr released > energt rcquired, the net Standsrd hent of combustlon is the amaunf of
lpat evolved whzn one mole of the stbsance wtder
result is thJebase of energy and the reaction is
slmdard conititiar.s (298 X, I bar pressure) is
erothermic.
ionplaely bwnt lo form lhe producr also under
The above point of view is further explained standari conttitians, h is representeil by 6If o
with solved examples in section 5.18'
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FIRST LAW OF THEBMODYNAMICS AND CHEMICAL
ENERGETICS sl23
Note carefully rrrd, i, it not lhe combusliofi ths, i! tion under these conditions is called stamlard
tuking pltrce at 298 K, whkh, in luct" cunny hop- enthalpv of lbrmation.
pen, It is lhe totul heal chunge that occurs whan
the
initiul reockurts u.ttd I&aI produc* ur6 et 2:lg t
irnttpeclive ol tht lrct thrl durin{ c4n b&ion,
temperatuft is higiEr tfun 299 K.
unt
C
the
thl
S
N
IA
IIT
2. Errthalpy ol formation.
The
,r'r,nditions r)l lctnpcrirlure Jnd presslrrc
trstr:rllyr'hoscn urc 2,)s K irnd I h r Drc\srrre Thi<
_ X AHi (Reactants)
*Aclually. A H"react.on Sum of enthalpics
= _ lSum
of enlhatpics
I ol r€acranr(
But if enthalpies of the ct"..-ne t"t"o
"." "s
r.,ol lh"n cnihalpy ;;;po]und = its cnrtralpy of fomsrior,
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Pradeep's
si24
Na++oH-+H++Cl--
Na+ + cl- + H2o , aH : -57'1 kJ mol-l
or H+ (aq) + oH- (44) ......._ Hzo O,
AH = --57 1 kJ mol-r
Thw ruufrulizalion is imply a rcaaion bawem
I,(s) whereas standard states for carbon and sul-
tlg H+ iortlt given b! tlu acid with tlu OH- ittns gitm
phur are C furaphite) and S, (rhombic) by ttu ba* ln lorm onc nwle of HrO* '
--6, we want to Predid the
enthalpy "*-p1",
"uppose The reaction
of combustion of methane' R
EE
IS
CH4 G) + z)r(s)'C(), Ul) +2HzO o
AR
''' AHo*r.tn'n
C
4. Enthalpy of Solution.
AH = _ 78.2 kl mol-r
IMPORTANT
; fi HrO 1/),
C
-
N
AH = I t1.7k.l
,. Thus it can bc gcneralizod thar thc process oI
dissolution is Lrsually enclothermic [or
sults rvhich do not form hydrates ljko n-aCI.
_-__. _(r)
KCll, KNO, crc.
(/r) hydrared salrs like CuSO4.5HzO,
CaCl2 . 6H2O etc.
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5126 Netu Course Chen istYq!
H:E+PV
.. AH= AE+ PAV+VAP
OXYGEN
FIRING
At constant pressure, AP = 0.
INLET
LEADS THERMOMETER Hence
AH:AE+PAV
STIRRER
At constant volums. AV = 0.
Hence AH = AE + VAP.
5.151. Measurement of Heat 0f
OUTER neutralisation. The heat of neutralisa-
INSULATED
VESSEL
t rn of an acid with a basc or vicc versa
can bc dctcrmined using a simplc
calorimeter consisting of a polythene
bottle* fitted with a cork having two
FILAMENT
holes, one [or the thermomctcr and the
,. other for the stirrer, as shorvn in Fig.
BOIMB
r:.1
(STEEL VESSEL) ofneutralisa-
5.13. Taking the examplc
tion o[ HCI with NaOH, the method
PLATINUM consists of the following steps :
CUP CONG.
KNOWN WT OF (i) A known volume oI HCI oI
SUASTANCE
known concentration (suy 100 cm3 of
0 5 N) is taken in one bcaker and an
R cqual volume o[ NuOH rrl thc samc
concentrltion (i.c. l00 cmr rrl 0 5 N; is
EE
FIGURE 5.12. Bomb calcrimeter. taken in anothcr bcaker.
AR
THERMOMETER
S
=fixroooxofJoules
5.153. Measurcment of heat of rractlon at .
follows -
Suppose the initial temperature of the acid
and the base tiC :
Final tempearature of the solution after
mixing = f'rC
. . : (t, - t,).C
Rise in tempemluls
Total mass of the solution : 100 + 100 = 200 g
tions, AH is negative whereas for endothermic
.'. Heat produced = x Specific h€at
Mass reactions. AH is positive, as already explained.
x Rise in temp. Alternatively, for the measurem ett ol qo ot
:2O0 x 4.lU x (r2-rr)J =rJ(say). AH, the reaction may be carried out in a vesselwith
This is the heat produced by neulralisation of
100 cc of 0.5 N HCl. 3i""Trtfi,3l
. . Heat produced by neutralisation of 1000
cc
of1 N HC'l (containing one gram equivalent of tcmperature may be recorded
R ,.otT:tl:h1
EE
calculated.
HCD
AR
heat of water is
qt absorbedby the
tyhat h,ould be the
ise is temperqdrre in each of the aboye cases ?
Solution. (i) 500 cm3 of 0. 1 M HCI
lgluiS". Rise in remperature
0.
:
300 78-294.05K = 6.73K = 1000
t
* 500 mole ot HCI
Heat transferred to the calorimeter = Heat
capacily of the calorimeter x Rise in temp. =0 0-5mole of HCI
= (8. e3 kJ K-r)
K) = 60. 1 kt
(6. 73
= 0.0-5 mole of H+ iom
200 cm3 ofO 2 M NaOH
Molar mass of CrHrt = 8 x 12 + 1g
: o.2
= 114 g mol-l I 200 mole of NaOH
.. Enthalpy of combustion 1000
= !3
1000 "
200 mole ot HrSO.
xsxAJ
O= r?r
= 0 04 mole of HzSOc (l
= 0 H+ ions
08 mole of ,r XJ
)19L
-*.
,100 cm3 of 0' 5 M KOH _ 0.78.
05 700x418 =
= 1000
, ,100 mole of KoH
h case (ii),healProduced = 4 568 kJ
0'2 mole of KOH : 45(18 J
=
0'2 mole of OH- ions Total mass of the solution = 200 + ll01)
=
Thus 0 08 mole of H+ irrns will neutralizc = 6009
R
EE
2O.O
C
S
N
IA
For examplc, the heat of fusion (AH1,,) ol ico For t]xample, thc heat ol vaporisatioll
(AH,.r,, ) ,rl rva(ir int,r its gascous:'lirte (steanl) ut
(m.p. :2'13 K) is 6 0 kl mol-r' It may he reprc-
rhe htiilirrrr l,oint r'l \tirlcr {373 K) is '10 kl'
7 lt mrrv
sented as ;
bc reprcscn'.ed as
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FIRST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS
I
coG)+; (),
N
07) G) (q),
-,corAH=
IA
-283.0 kJ mol-!
IIT
c(s) e-j-rJ
AH=-3s3sk.r
._.
Thus the total heat evolved in the two steps
= (-
_
will be AH + ( -283.0)
the statrdard s(ate conditiotrs, superscript e is
0.5)
kJ mol -r which is thc same whcn the reactioD takes
=- 39315
used with H, r'.e. we write,
place directly in one step.
A,He, A"Ho, ArHeetc. However, more (2) Sulphur (Rhombic) burns to form SO,
common way of representation is AH", AH7 etc.
or directly in one step as
AH"', AHr'etc.
s (R) + C)2 G)-....- so3 (s),
law ol Constant Heat Sumrmlion ;
G.H. H AH = _395.4 kJ mol_r
gave a law about Sulphur may change to SOt in two steps
as
of experimental
after his name as
(,) s (R) + oz k)- soz G),
AH = _ 297.5kJ mol_r
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Pvadecf 's Neut Course ChemistrgVffi
5/30
be
a number of times, a large amount of heat cun
crcatecl. This is, horvcver, against thc luw of cttnscr-
vation of cnergy. Hcncc Q nrust be equal to Q' i r'
Hcss's law must be correct.
S(R)
B --+ c-
tion of nrethane (CHo) frtnt thc followirtg tlotu :
A- D
AR
SuPpose the heats evolved-in these three st eps (i) C (i) + o2G) Co, G) '
C
""",""1f,11"1,i,,11; I
+
IA
O, (sl (l\
tii) H,lg) + ; H ro .
IIT
"
= _2u5.6H rtnt-l
*
(iii) CH 4 @) +2o CO 2 G)+2H ro (t)'
2 @)
-'
LH=- l]90'4Hntol-l
Solution. We aim at
zG)- cHa (q) ; AH = ?
=- 74 9 kJ mol-l
or C (s) + 2H, (q) -- CHo G) ;
AH = -74 9kJmol-l
Hence hcat oI formation oI mcthanc is
-1
Atl/ = - 74 9 kJ mol
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FIRST LAW OF THERI\,IODYNAMICS AND CHEi,4ICAL ENERGETICS 5t,,
laXAl\IPLD 2.Calculote the mthaw offonna- AH = -393 -5- (- 395.4)= a19L.I
tion of carbon monoxide (CO) lron lhe lollowinq or C(graphite) C(diamond);
dote :
(i) C(s)+ or(9- CozG); - aH = + 1.9kJ
3. Calculation of the €nthalpy of hydration.
A,H=-3933klntol-l The experimental determination of the enthalpy of
I hydration is almost impossible. However, it can be
tii) Co \gt + ror(g\- Cor(gt; easily calculated using Hess's law as illustrated by
the following example :
LH = - 282.E kJ mol-1
Colcltlote the enthalpy of hydra-
Solution. Wc aim at
tion of anhydrous copper sulphate (CuSOr) into
1
C(s)+ 7orfu) ' co(c):AH=? lrydrated copper sulphate (CuSOo. SHrO). Given
tltut the entholpies of sohttions of anhydrous copper
Subtracting equation (ri) from (i), we get sulphate atrd )tydrated copper sulphate are 66. 5 -
I
+ rorG)-coG)-
C(t) 0r and * 11.7 kJ mol-l respectively
Solution. We are given
AH=- 393 3-(-2f,2'8) = - 110 5kJmol-' (i) CUSO, (s) + aq """""'r CuSOn (aq) ;
I
or C(s)+;OrG)........- COE); AH = - 66.5 kJ mol-r
as=-riosu. (ii) CuSOo . 5HrO (s) + aq-
. . Heat of formation o[ CO is CuSOo (aq) ; AH= + 11.7kJmol-1
AH, = 116 5 1t' to'-' R
EE
We aim at
CuSOo (s) + 5HrO (/) .*
AR
heat and is a very slow process. Hence the ex- (iil) CuSOn (s) + 5HrO (/) -----------+
IA
enthalpies of fomwtion of COrand H2O arc 394 5 AH= -393 4 +2 (-285 7\-(-890 2) kJ mol-r
qnd 286'6 kJ mol-l respectively, calculate the en- = - 74'6 kJ mol-r
thqlpy o[ Iomtation of ethyl olcohol. Hence the heat of formation of methane is
We are given :
LHI = - 74 6kJmol-r
I.IXA\II'LIi -1. Calculate tlu heat ol fonnation
(0 qH5OH + 30, + lQ92 + 3HzO,
of KCI fronr the following dota :
AH = - 1380 7kJ mol-l (i) KoH (aq) + HCt (aq)
(rD C + Or-CO, AH= -394'5 kJ mol-r (l), --,57'3Hmol-1
, KCI (aq) + HrO LH -- -
I 1
(i,r) H, + * or.....-- Hro, AH=-2a6 6 kJ mol-r (ii) H2w) +
)Ortel- U.rO (t\,
-
In order to get this thermochemical equation, ll
multiply Eq. @) by2 and Eq. (ir'i) by 3 and substract (iv) K(s) + !2o2 (E) * rH rte) * oq
C
+ 3Hz*
1
qH5OH LH = t 18'4 kJ mot-l
IIT
2C
iO, --- I
-
Soluton. We aim at
aH= (-3e4'5)+3 (-286 6)-(-1380.7)
2 I
= - 268 1 kJ mol-l K(r)+ Cl, (8)"""+KCl (s). AH=?...(t'i)
Z
Thus the heat of formation of ethyl alcohol is In order to get this thermochemical equation,
AH, = - 266 we follow the following two steps :
Il\ \)lPl ',O',tot-'
ll-1. Calculate the enthalp of fonna' Srep 1. Adding Eqns. (rii) and (ir') and sub-
tion of methane, given that the enthalPies of combus' tractiug Eq. (v), we have
tion of methane, grqphite and hydrogen are 890' 2 kJ' 1l
K(r)+ (s) + H2 G) + o,
i9j'4 H and 285'7 H mol-l respectively. ;Cl, i Gl.........-
We are given : KCI (s)+HCl (aq) + KoH (rq) - KCI (aq)
(,) CH4 + 2Or-"- COz + 2H2O, AH= - 487.4 + (- 164.4) - (18.4)
AH = - 890 2kJmol-1 = - 670 2 kJ mol-r ...(vii)
Step 2. To cancel out the terms ofthis equation
(rt) C + oz COz,
which do not appcar in the required equation (vi),
-' AH= -393'4 kJ mol-r add Eq. (i) to Eq. (uii) and srrbtract Eq. (ii) from
l their sum. This gives
(iiil H2+;O2 -'--- H2O
' 1
K (s) + Cl, G).-.......- KCI (r) :
AH=-285 7Umol-t ;
We aim at : LH= _ 6i o. z 51,1; j
C + Ztl, "'-------+ CHl AH : ? _+ l;T; :
'
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FIHST LAW OF THERMODYNAMICS AND CHEMICAL ENEBGETICS s/33
l ltthylene on combustion gives carboD dioxide and 2SO2 G) + o2@) * 2SO3 G),
water. Its enthalpy ofcombustion is 1410.0 kJ/mol.
If rhe enthalpy of formatioD of COz aod I-I2O are AII " = -198 kJ nrol-l
393.3 kJ and 286.2 kJ re.spectively. Calculaie the kl mol-r]
col halpy of formation of ethylene.
[ "ns - '145'9
7. Calculatc the enthalpy oI formation of anhydrous
[turs. +51.0 kJ Erol-ll Aj2Cl6 from lhe follo\rying data :
2. Calculate the
enthalpy of formation of carbon
(i) 2Al (r) + 6lrct (aq) ......-
disulphide given that the enthalpyofcombusrion of AlrCl5 @q) + 3l1x@) + r 004.2 kJ. kJ nlol-r
carbon disulphide is ll0.2 kJ mol-l aDd tbos€ ot
sulphur and carbon are 29.4 kJ aod 394.5 k g (,,) H2 G)+cL (S) .+2HClE)+184.t kJmol-r
atoD'r rcsp€ctively-
[,\ns. - t79.1 kJ mol-11 01i) IICI G) + aq l }ICl (oq) + 73.2 kJ mol-l
3. (hlculirtc the cnthalp) of formation o[ acetic acid (iv) FJ2CI66) + aq
lion] the fbllowlng dalr : -
Aj2 Cl6 (d4)+643. r kJ mol-r
(l) (l (r) + c)2 G) ......* CO2 G), AH =
-393.7};I I,\trs - 1352.6 kJ mol-ll
tii) II2 (s) * i o, (Xr .... H2O 1lr. E From the tollowiDg I hermochemical cquations, c{l-
culate the standard erthalpy oI formatioD of IICI (s).
aH = kJ (A) H, (B)
(,iD cH3coolt (/) + 2o2G)
-2a5.8 R 2H (s),
EE
- all = +436.0 kl mol-l
zCOz G) + 2H2O (l),- = ---873.2 kJ
AR
AII = +431.8 kl
(L rzl122 Ot l) tiom the lollowing data :-
IA
{iii)ll, +
0i)c(.') + o2@) coq @),
I\Ds.- 2677.1 td Itrot-rl - AH = - 405.4 kJ mol-l
S. (hlculatc the eothalpy of formation of benzcoe, (iii) 2H2(8) + or(g) ?llr0 (1,
glvcn that enthalpies of combustion of benzcoe,
carhoo and hydrogcn are kJ, kJ -
AII = - 572.4 kJ mol-l
-3281.5
lD(l --286 I kJ/mol, respectively. -394.9 On lvhat law areyour c{lculations based ?
1r
AH=-3945kJmol-l +;cr2 G,).-
S
Eq. (iii) + 2 x Eqo. (ii)-Eqn. (i) Sives the required 9. Aim: 4 C (.r) + s H2 G) * E), AH=?
IA
C4H1o
result.
IIT
<1
3. Ainr:2C(,r) +2HzG)+ 02G)- CH3COotl, 4 x Eqn. (ii + i x Eqn. tiii) i x Eqn. (i) givcs
tion ol ethylene (gas) to form CO, (gas) and HrO QHo G) + 302(0 --....--..,
(i,) H, G) +
1
o, G) -._....' Hzo (8),
-2c - zHz@) - CzHq(c)
(s)
i 3o2@)-2coz@) + ZHzO (9 - CzHq(B)
AH = - 241'8 kJ mol-r or QHo @) + 3o2 @) @) +2H.2o G)
-zcoz
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FIRST LAW OF THERMODYNAMICS AND CHEMICAL ENEBGETICS 5/35
1. Calculate the enthalpy of combustioo of beozene 3. Calculate the enthalpy ofreaction for
fronr the followiDg data :-
(i) 6C (, + 3H2 G)-C6H6 (0, CO(a)+Z02e)......* cO2G)
GivenC(r) + o2G)
AH =49.0 kJ mol-l
(r:HrGl* I or@;*Hzo (0,
-COzg}
AH = 5 kJ mol-1
-393
* ._
AH = -28i.8 kJ mol-l
c 1r; ] o, rg; Co G:)
^H
=-110.5 kJ mol-r
[ kJ
-3242.2 C(graphite) + oz G)
S
-74.8,
yJ respectivefy. Calculate the-393.5
eDthatpy of
IIT
-246.2 co()*lor@)
combustion ofmetbane at ordinary temperature. coz@) + 283 okJmol-l
[ \ns
-Egl.l kJ mot-l] -[ \rr. dH 110.4 kJ mol-11
= -
H lNT5 FoRDtFFlcuLT
r. Ainr : c6H6 (4 + AH nerction
"Rortr:vo
=
[^Hi(Co2) aHi(HzO)l +z
+ 02 G)
6 CO2@) + 3 H2O (/), arr = ? _ - l^Hi(CH4) + 2 ^Hi(02)l
-
6xEqn.(i)+3xEqn.(ii) 4. Aim : C (.r) * o, €1- CO (s.). 6H = ,
|
(i) givcs the required resutr. Eqn. (r)-Eqn. 0r) gives the required resutr.
-Eqn.
2. Aim I CHl e) + 2 o7@)- CO, (g) + 2 HzO (l)
f
, \..\\ ll,Lla. Given rlr e followingthermochemi_
LH : - 300.0 kJ mot-\
cal cquations Cqlculqte LH for the
(i) S (rhombic) + O, (g) SO, (g), gtqm om o[ rhombic sulph
phur
AH : --.+
_ 297. 5 kl ntot-r
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s/36 Pradeep's :r: a:i i!i/,i;t;lth'lsttglfi[)
Solution. We aim at : or S(rhombic) -.--.------ S(monoclinic),
S(rhombic)--' S(monoclinic), AH :? AH : +2.5 kJ mol-r
Equation (i) -Equation (ii) gives Thus for the transformation of one graul atom
of rhombic sulphur into monoclinic sulphtrr, 2'-5 k.l
S(rhombic) - S(monoclinic) -.-- 0,
mol- I of heat is absorbed.
LH = 297'5 - (- 300'0) : 2'5 kI mol-l
!lil
l.\ \\ll'l.l'. Enthalpy of solution (LH) for AH: AHr (say) ...(iy)
BuClr.2HrO and BaCl, are 8'8 snd - 20'6 kl BaCl, .2HrO (s) * uq BaClr(aq) ,
ntol- | respectively. Caladate the heat of hydration of AH = AHz (say) ...(v)
-
BaClrto BaClr.2H2O. Then according to Hess's law
_q[!g"r We arc given AHr+AHr=-20'6kJ
(i) BaCl, .zHzO (s)+ aq BaClz(aq), But AH, = 8'8 kJ mol-l
AH : 8'8 kl mol-1 ['.'Equation (i) : Equation (v) |
(ii) BaCl, (s) + aq -----_- BaClz@q), .'.AHr = -20'6-8'8= -29'4kJmol-l
AH : -20'6kJ mol-l But Equation (iii) : Equation (lu)
We aim at Hence the heat of hydration of BaC)I,
BaCl! (s) * 2H2O+ BaClr.2HrO ('s),
(CuSOo.5H2O) are --{6'5 and +11'7 icJ mol-1 respectively. Calculate the enthalpy
of hydration ot
TYPE V On thc calculation What is LHo aa 25'C lor this reaction ? Given
ofcrtthalpy charge for any rcaction that the standard heats of Iomation of AlrO, and
@i) -........+
2Al (s)+ Fero. G) ...........+ Ato: (.r)+2Fe (s),
N
IA
cH4 g) + 3cr2 cr) ...* ana,rl,) t ,r., n, StaDdard enthalpies of formatioo (AH/) at 25' C
| \ \.rlf t,l i. The heat evolvedin the combus_ Hence O, used in the production of 44-5 15 kl
S
of heat at STP
IA
CH1@) + 2oz@) Cor(s) + 2H2o (t), i \{\tf'l-f ). Thc heat evolveditt the combus-
IIT
-
LH: : * 19fi72 joules/mole
AR
_ 1667.8H mot_1
C
-
!g!Cqg.. (a) From the lust given equation
2 -g1." nf Al (i.e. 2 x 27 g
..- -. = 54 g) on com_
Dusrron grve heat = 1667.g kJ
. . 1 g ofAl on combustion gives heat
AE = _ 2500 U.
1667 .R
-'54-= o
30 9kJ ^ ,fo. Iost =ofl00
(Cr2H2zO1)
loss 1632 kJ of
g (given)
energy, sucrose
:
1poni, )n"'gt/time'
lw = lts-l) 39500 J
395 s
(N.C.E.RT.) =
100 J
AH = kJ mol-l
-2-1
to Co2
(a) Catculate AH for burning ofdiamond R
EE
th hite that rnust be
(b) Calculate
AR
6.
2. Crmpare the quantity of heat p-roducedwith thar ir'Jti* as
reaclion reptesented
N
follows :
r 3 Br2() ...
IIT
2P (s) 2PBr3GI)'
l. (a) Eqn.p))-Eqn.
1j; gives ttre re[uireO resutt.
(b) 393.7 kJ of heat is produced froDr
fh: l_ 9" of ,
graphite Eotc (lt(] g)"orr,urpy "r,rnfiGiffiuoion
of gtucce. Hence for 18 I gtucce,
= 12& AH=+2t4td
. . 500,0 kJ of hcar will b€ produced fiom graphite 4 (a) I Mole ClHto = 58g,
72
- 3!3? x s000 6 = 1s2.4 a ... Hear p.oduc€d from l12c{ g
2. C5H,rOa + 6 Or+ 6 CO2 + 6H2O 265A
=-5E- x r1200 = 513 8.9kJ.
& Rcacron = [6 AHi (CO, + AHi (fLO,
6 No. ofda)s for which it will tast
_
[^Hi(c6Hr2o5) + 6 Mifqli j
= 513268.9D.n,@O = 25. dara _ 26 days
(D) After wastage, heat avaitabte
= [6 (- 393.5) + 6 (- 28s .s)] _ (_ 1260) + 6 (0) 67
= - 2816.4 tJ mot- I = ;05- x 513268.9 = 343890 kJ
.. Heat produced from I g gucose No. of da)5 for which it will tast
2t16.4 = 34389020000 = 1? dals
= -116-= ts ou
5. Mot mass ofglucose (C6H12O6)
CtzHzzOtt +602-*6CO2 + 1l HzO 180. =
Glucse required per day
aHn."cr;,,n = [6 (_ 393.5) + t I (_
2s5.9)]
= (lE0 ,/ 2900) x 10.000l!.
- I- 2221 + Ol R
6. RequLed AH =ff"z.utt J,o , *r.
EE
= - 3284.9 tJ mol-l 7. For evaporarioo of I ia
AR
32A4.9
= 1;;- u = e.6 kI
.. For cyapomtion of 80 g of H2O,
heat required
S
40.79
_lE_
N
6 COz@) t.
IIT
l r, r, * ) ru ro......- r.r,rl, A H = A Hr
.'. AH =I B.E. (Reactants)
lolytron. First Method. By using the rclation I B.E. (products)
MReaction = 2 LI/., (producs)
_ E LIf (Reactonts) = j a.e. 6,y +
I n.E. 1cry - B.E. (HCr)
,
Here we are given
H, G) .-...} ZH(g),AH = +430Umol-r - ", = + , +to * lx 2a2 - B.E. (HCt)
. 8.E. (HCl) = 21.5 + 72t + 9t
ct,(g) '-+ zcl(g), AH : + 242 kJ -;;gl
= 427 kJ mol-r
,i
"'(")
we aim at of
Hcl G) ---.H G) + cl (s), AH = ? ...(nr) dissociqtion of H2arc -74.8, +7j9.6and435.4kJ
Evidently, for reaction (rrr) mol-1 respectively.
AH:>AH/' (products) - XAH/. (Reacrants) Solution. Here we are given
= [AH/'(H) + AH/" (ct)l - taH/. (HCl)l c(r) + 2H2
k).-......- CH1 k),
-'(iv) R AH : - 74.8 kJ ...(,
EE
(,),
From equation^s (i) and cG)----------+ cG), AH = + 71s.6H ...(ii)
H.(s)- 2H k), au : + 435.4H
AR
... (ni')
H/'(Cl)=
1
We aim at CH4 +
S
A k) --.......r C (S)
){+ztzuy= + t2r kJmot-r 4H(S)
N
.-(iv)
IA
Also we are given AH/ (HCl) =- 91 kJ mol-t Eqn. Q;) + 2xBqt (iii) _ Eqn (r) gives
IIT
-
Given thot the bond enthalPies H-!1\ arc-'it -6n, )olcuiate rc change l enthalpy
'f
Br are 435, 192 and 364 kJ mol-' following reaction :
Br- Br and H - 'for theirnrtsl+5oz@)
re spectivelY.
Soluiion. Energy absorbed for dissociation i Co2 @) + 4 H.O (g)
(Products) mol-r
= - 1662 kJ
N
IA
IIT
=
IA
-rso=rBE
.
"-ffi Etr*t--
. r\er energy released q2g
mot-l
=
= 249kt
_ 679
E. Let us catcutare
-tr,"."
a,
(.-;)'z.BrE;(:"--?]
,o. ,n" ,"r*",1o1 "E
(N-H)J
Le. AH = - 249 kJ mol-l H H
Arternativety, aH = B.E. (H2) +
+ (o,B.E. qH6@) i.e.r_*_i_" O, .... 2c(s) + 6 H G)
_ 2 B.E. (o_H)
AH
*+x4s2 -2 x464 = - 24ekJmol-r. 2x Eqn. (r) +3 x Eqn. (rrD-Eqn. (i)
. :ot, gives
4. For reaction (iO AHReacfion
=?A25.,7j kl
AH = B.E. (H, * |zs.1or1- 2 B.E. (o -H) If, is the bond eners' of c--c bond, rben
ji::ir:i:i::;t::l:jti:t:till:lii::ji::iiii:i::.i::l::rji:iiii:i::'lil:ji:iijiii:lii:::i1:ii;iiliiiilil:;i:i1:;:ii:i:il;il::Ii:;i!:l:jr:1:i
AD.D TO Y U.R
comPounds wh e those
H1. rhe mmPounds whi:n nL" *qlllY-",:t5,1:[il:iilHnl"'":[rTJd,exothermic
with posiiNe enthalpies of formatron are
ca :::-..^,,^..
#2. VariationofheatofreactionwithtgmPeratureisEivenbyKirchoff,sequatiollviz.
7s 14 kr
,.r. au7{u+ (a{) + ^Hi(cl- (d4) - ^Hi(HCl G)) = -
C
get
But alri(HCl(8)) = -92 30 kJ' Putting the values'we
S
N
0+
-
IIT
(cl (44)) = 44 YJ
or AH
i -167 atomicmolecule
is nearly halfof th
ia, J EnthalPy of formadon of an aiom
e.g.H2@)'z]H(s)' AII'= 435 kJ mol-l
halPy of solution
quation (relating
tioD is
+-+l'l
q are solubilities at temPeratures
i' and T' respectively'
where Cl and
form
mation is takenaszero for the allotro-pic
,, Enrhalpy of ionization of a weak acid can be calculated by subtracting enthalpy of neutralisation of that acid
with a sirong base from 57 .7 kJ e.g. heatof ionization of CH3COOH:57.1 *55 2=I 9kJ
Likewise enthalpy of ioDization of a weak base can be calculated.
rr Enrhalpy of neutralisatiofl of HF is about 68 kJ i. e. n]ore than that of a stronS acid with a strong base viz 57. 1
kJ. This is due to very hiSh hydration eners/ of fluoride ions.
: AHm.uustion is always negative- Hou,ever, there are some reactions which involve combiDation with oxygen
leading to partial coDrbustion but AH is positive e.S Nz + Oz + 2 NO, AH = +ve
Further wheo F2 combines with 02 to form OF2, F2 is reduced and not o(idized and AH for the reaction is
positive
We need energy almost in every sphere of heat energy produccd by burning of coal may be
C
ent upon energy. In fact, tbe progress of a country turbine and produce electricity. This is the prin-
IA
it consumes as it is an indication of the industrial The sudden sharp rise in prices of crude
progress andthe progress ofliving standards ofthat ' petroleum by oil producing countries in the mid
country. 2000 and tbreat from global warming. rising sea
levels and climatic changes due to green house gas
In this respect, India is still backward as the
electrical energy consumption per person is quite emissions from fossil fuels forced the countries
low as compared to the developed countries. Afew across the world to think of alternatlve sourcts of
energy i,e. non- conventional all.d renewable. Afew
sources of energy are briefly explained below : - of these are given below.
1. Fossil fuels. Coal and petroleum which are
2. Dung and wooil. This is another very cheap
believed to have been formed from animals and
plants that remained buried uader the surface of and easily available source of energy. Gobar gas
plants are becoming more and more popular in the
the earth for millions of years where they were
subjected to high temperature a.nd pressure are rural areas which make use of cow-duag and
decayed plants.
called fossil fuels. These are the most commonfuels
at the disposal of man and hence are call ed conven- 3. Water. Falling water has high kinetic energ5r
tional fuels. In India, nearly 907o of the total energy which can be used to run the turbine and produce
requirement is met by these fuels. The various frac- electricity. This is the principle of hyilro-electric
tions obtained by fractional distillation of crude powet stations set up at Nangal and
petroleum (e.g gasoline, diesel oil, kerosene oil Shivasamudram.
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5148 Pradeep's,:!.t il11;,;,, 1,:,.€_Ai.Ai-i lAD
4. Radioactive elements. A small amount of a earth's interior in the form of hot springs. The heat
radioactive element such as uranium when under- of these springs can be utilized as a source of
goes nuclear fission produces a
tremendous eniergy. There are some places where people cook
amount of energy which is equivalent to the energy their dishes in thehot water springs.
produced by the burning of thousands of quintals 7. fidal waves and ocean currents which pos-
of coal. Hence every country of the world has been sess high kinetic energy can also be e4ploited as a
trying to harness energy from this source. The source of energy.
plants which work on this principle are called In India, coal has been the main source of
Nuclear power stations.In India, we have nuclear energy. It is only during the last few years that Oil
power stations at Thrapur (Maharashtra), Kota and Natural Gas Commi"ssion has made a break-
(Raiasthan) and Kalpakkam (Tamil Nadu). through in the field of petroleum. After inde-
5. Wind. This is a gift of nature. The use of pendence, considerable development has also
wind mills has been quite common but this source taken place in the field of hydroelectric power as a
has not been exploited fully yet. source of energy.
6. Geothermal sources. The interior of the The ffierent sources of energy consumption
earth is very hot. Hence, at a number of places, we in India and in the world, as they existed in 1,998,
find hot gases and hot steam rushing out of the are shown in Fig. 5.15 below :
INDIA WORLD
COAL (55'20/6)
orL (3s%) RENEWABLES
R (2./")
EE
HYDRO-
AR
ELECTRIC
(2o/o)
C
NUCLEAR
S
ENERGY (1%)
IA
RENEWABLES
(3o/6)
IIT
5.20. The Sun as the Primary or (iii) The heat of the sun causes rain and hence
Ultimate Source of Energy :iti;r.;iil, :ii:ii::::i:
we have water-falls acting as a source of
The various sources of energy such as fossil hydroelectric power.
fuels, wood, hydroelectric power, wind power, (fu) The heat of the sun causes winds, tides
nuclear power etc. are ultimately dependent upon and ocean waves.
the sun, e.g. (v) It is believed that all elements including
(i) Plants grow by synthesising their food in radioactive elements like uranium are synthesised
the presence of sunlight (photosynthesis). from hydrogen by the process of nuclear fusion
(ii) The plants (forests) are then fossilized to taking place in sun or other stars.
form coal or they are food for the animals which in Efforts have also been made to explore the
turn are a source of gobar gas or are fossilized to solar energy for generating electriciry. However,
form petroleum. these efforts have not met with any appreciable
success so far.
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FIRST LAW OF THERMODYNAI\,IICS AND CHEMICAL ENERGETICS
WNDS, TIDES
OCEAN WAVES
GROWTH OF PLANTS
BY PHOTOSYNTHESIS
fog
MARINE ANIMALS
R
EE
FOSSILIZED TO
PETROLEUM
AR
C
1i:l{jiif.}€i*?.in:.riftrirriii,irii
oxygen to the different parts of the body.
For the product.ion of electricity by the ther- (ili) Oxidcs ofnltrogen and sulphur. They are
mal power plants and to meet the ever increasing corrosive and poisonous. They dissolve in the rain
needs of trarsport in the cities and towns, the con- water thereby making it acidic. This is called 'acid
sumption of fossil fuels (i.e. coal a.ud petroleum rain'.It damages the stone buildings andforqsts and
products) is on the increase. The combustion of also the metals.
these fuels produces carbon dioxide, carbon (iv) Unburnt bydrmarbons. Some of these
monoxide, oxides of nitrogen and sulphur (by
hydrocarbons are a great health hazard and may
oxidation of compounds of sulphur and nitrogen or
even cauie cancer.
elcmental sulphur present as impurity in the fossil
fuels) and somo unburnt hydrocarbons. All of these Besides fossil fuels, another very important
are the pollutants of the atmosphere as explained sourc.e of energy is the 'nuclearfuel' being used in
below : the nuclear power stations, This sometimes causes
(i) Carbon dioxide. This is the main product even greater problems. A.lthough the release of
of combustion of the fossil fuels. If its percentage radioactivity into the atmosphere is strictly control-
in the atmosphere increases beyond a particu.lar led, yet disasters do occur sometimes. For example
level, the climate of that place may ch aage e.g. ttLe in 1986, such a disaster took place in Russia (in
average temperature may increase+. Chernobyl). A very large number of people are
(ii) Carbon monoxide. It combines with the affected when such a disaster occurs, The storage
haemoglobin of the blood forming carboryhaemo- of radioactive waste (produced by the nuclear
tThis cffc.t i6 csllcd '8rctnhoosc cftcct, (iis-cusscd in Unit 1E).
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s/50
power stations) which has still a very high radioac- parts of plants and animals. When allowed torotten
tive level poses a very serious problem. in the absence of air, it decomposes to produca
biogas which like natural gas can be used as a
Scientists all over the world are working to
domestic fuel or to produce electricity. The residue
control the pollution. Many advanced coutrtries
left contains a high percentage ofdtrogen and can
have already achieved a significant success. In
be used as a fertilizer.
India, efforts are on to rninimize the pollution.
(3) Coal. Coal as such has the problem of
5.22. Why Energy Crisis-Alternativc Sources of transportation an The im-
__!1"lgy- -I : " 1!l e 9I:9 !i"3!:" purities of sulphu it is con-
o"rr"rgy
The various so*""s, as discussed verted into a gase c natural
above; may be divided into two categories : gas which can be easily transported in pipe lines.
(1) Renewable (Non-depletable) The product contains a mixture of CO, [I, and
(2) Non-renewable (Depletable) CHn all of which can be used as fuels.
Renewable sources include wood (plants), (4) Hydrogen. It has high heat of combustion
wind, falling water, geothermal Power, oc€an and does not create any pollution problem. Its use
waves, tidal waves, solar energy etc. These sources as a rocket fuel is well known. It can be obtained in
are produccd coatinuously in aatue and are aLnost large amounts from water. It can be used as a good
inexhaustible, at least so long as the life exists on fuel for production of electricity.
this earth. (5) Nuclear enerp. As already metrtioned,
Crude oil (petroleum), natural gas, coal, radioactive elements such as uranium and
uranium etc, are non- renewable energy sourc€s as plutonium are a potential source of energy which
these have accumulated over ages and are not are being used to produce electricity.
R
(Q Other sources, These irclude geothermal,
EE
quickly replaceable ufien they are exhausted.
The rate at which the non-renewable sources wind and tidal waves and ocean currents.
AR
of energy are beiag consumed, it is expected that However, we should also try to conserve ener-
gy as far as possible. A few practical suggestions
C
It may be pointed out that the law of conser- (2) Use high gffiglsncy oil or gas stoves which
IIT
vation of energ5r does not fail here. The only prob- burn the fuelwith a blue flame and not with a yellow
lem is that the combustion of fuels is a one way flame (which is an incomplet€ combustion produc-
process i.e. either tho products of combustion are ing less heat).
not converted back into the original substances at (3) Keep ready the next item to be heated,
all or they are converted back at a rate much slower otherwise, put off the stove.
than the rate of their consumption. For example, (4) Usethe vessels with flat bottom for heating
coal burns to form CO2 but CO2 is converted back and not the vessels with round bottoms.
into carbon by nature tlrough photosynthesis at a (5) Use energy-saving devices for cooking like
much slower rate.
Pressrue cookers etc.
Foreseeing the problem of energl crisis, (6) Switch off the lights, fatrs etc. when not
scientists all over the world are trying to find ways
required.
and means ofgetting all types of enerry &om altcr-
1 native squmu'i.e. renewable and non-convention-
(7) In winter, better sit in the sun to warm
yourself in-stead of using heaters inside the rooms.
al sources. A few of these are given below :
(1) Solar cE€r1EI e.8 in the form of solar (8) Use casseroles for keeping the eatables
' Lbokers, solar water pumps, solar photovoltaic hot instead of heating them again.
ce.lls, solar water heaaGgisystems etc. (9) Thke bath with fresh running water instead
(2) Blomass. It is thB waste material obtained of using geysers.
from animals and plants e.& cattle dung and dead (10) Plant trees ifyou have surplus land.
.To tap altcmati!'c sourtts,India has set uP Min for Non-Crnvcntional Encrry Sources (MNES).It has tapped ncarly
.all sou{tcs likc solar, xrind, biomass, hydro Projects etc
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FIRST LAW OF THEHMODYNAMICS AND CHEMICAL ENEBGETICS 5/s1
(N.C.E.RT)
C
, Q. ?. Why'Kelvin scale of temPeraturd is called rAbsoluae scale of temperature' ? What are the reference poitrts
N
on this cqle.
IA
Ans. On ihe Kelvin scale of temperaturc, zero point is tbe loweit p6sible temperature whereas on the celsius scale,
IIT
zero point is only with referenc€ to lce point. Hence the former is called absolute scale. The reference poilts
are absolute zero of temperature and the triple poiDt ofwater (0.01.C or 273. 16 K).
q) $ Ca[ the absolute volue of internfll energy be determined ? Why or why not ?
Ans. No, because it is the sum of different typ€s of energies some of wbich cannot be dctermlned.
(.) e One mole ofCO2 at 300 K aud I Atm pressure is heated
iD a closcd vessel so thot temp. is 500 K aDd prcssure
is S atm. Then it is cooled so that tcmp, is joo K ond pr:essure is I ath. Whotis the change in internnl encrgjr
ofthe gns ?
Ans. No chaoge because internalenerry is a state function.
(J Irr \lhter derDmPces by absorbing 256 2 ofelectri.fll etre45/
kl tEr Elole. When H2 and 02 conbi1e to form one
mole otHrO, 2E6 2 (l of he{t is produced. Which law is proved ? Whst statemeht o[ the lnw follot s from it ?
, Ars'Law of conservation of ener$/ or l st law of thermodynamics. Def, Energy can nelther bc created or destroyecl,
although it may be converted from orle form to another.
i., I L N.itherq nor'l, is:r state function. yet{ + l/ isa state function. Explsitr why.
ADs. .1 + r, = AE and aE is a state functioo.
{l ll Why heai is not a st{rte function ?
Ahs. According to first law of thermodynamics, AE =q +w otq = AE
-,r.AsAE is a state fuoction but l, is not
a state function, therefore q is also not a state function.
r., I 1 Why absolrte vahre of enthalpy c[nnot be determined ?
Ans. As H = E + PV and absolute value of internal eDergy, E €nnot be determined, therefore
absolute value of
H caDnot be determined.
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Pradeay's Ncttt Courcc Chc-istrg@
sl52
t.t I J Whot is thc relation between AH atrd AU ? Undet what condition, the two ate equal ?
Ans. aII = aU + PAV = AU + A rr Kf For conditioDs see page 5/14.
-) I5 Explain why heat caPacity is not o st tc function'
Ans. Heat capacity (C) = As'4'is not a state fuoction, thcrefore C is also oot a state function
#.
(l Ic Derive thflt for an ideal gag C, =dE/t df,
^ndCp=dH/
AIls. Seo page 5/17.
(l ll Specific he{t ofl-i (s), Na (s), K (r), Rb (r)andCs (r) rt 39E K arc 3 57, 123,0 756,0 363 and0 242
J g-r 6-t r-espectivella Compute the holar heat capacities of these elehents oud identify any Periodic
i.ina. It tt i" t.en<I, use it to predict the molar hest copacity of Ft' (N'C'E'tr.T)
""" "
Ans. Molar heat caPacity = sPccific heal x Molar mass
1
Heoc€ for U, Na, K Rb aDd Cs, their values (JK- mol-1) will be rqspectively
3'57 x'l =25 0, 12ix23=2A 3, 0'756x39=29 5, 0 363 x85 =30 86,
t
JI i
Why some reactions are exothermic while some others are erdothermic ?
S
Ans. lfthe total internal energ)i of the reactanls (ER) is greater than that ofthe producLs (Ep), the eners/ is released
N
and the reaction is exothermic. However if ER < Ep, then energy is absorbed and the reaction isendothermic.
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Atrs. No. It will b€ greater in case (D) because when H2O (8) condenses to folm Hzo (D' heat is released-
{). 2.1. Which of the followitrg ls/are exotherDic and thich igare endothcrmic ?
(i) ca ...- c"2+ g1 + z (ii) o G) + e- o- (S)
@) "-
(iii) N2- G) + ,- .....- Pr- g1 -
Ans Endothermic (ionizition energy
(i) is required)
(ii) Exothermic (first electron affinity is energy released)
. I x.-
Heal ofevolved from mole = kI
Z A
Heat evolved from combustion of 1 mole of C to CO = 110 5 kJ
.. Ileal evolved
I llo 5
from mole = -i = 55 25
Z
;+ 55 25 =252 or r=393.5kJrnol-t.
Q. 26. The enthalpy ofcombustion of glucose (CfHl2Od is 2E40 kl mol-l.lYhat is i(s cslorific valuc ?
(iii) The enthalpy of solutior of BoCl2 (r) and BnCl, . 2IIrO (s) a.e r and y kJ mol-l respectively. Then
enthslpy of hydration ofBaCl, will be.........
Ars' (i) exothermic, endotherD]ic (ii) AH,"porir"rion R
(iD) (r - r) kJ ol - 1.
EE
m
Q. 29.
t
hy boDd enerly is t{ken as an avcragc value ? ExplaiE with a suitable example.
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ADs. The bond eners/ of the same boDd iII different polyatonric moleculcs is not sanle e.g. bond energy of C-Cl
C
boDd in CH3C|, CH3CHzCI etc. is nol same, Even in the same polyatonic molecule like CH4, the boDd
S
ener$/ of all the four C-Il bonds is not san]e. Hence an aYerage value is taken.
N
Q -rl The enthalpy ofneutralisatior ofacetic acid by KOH is -55 tklmol-l while thst of hydrochloric ,rcid by
KOH is kJ mol -', Why are tley ditfereDt ard what does the dilTerence represent ? (N.C.D.R,T)
-57.3
Als. Heat of neutralisation of acetic acid $ less than that of HCI because acetic acid is a weak acid aod does not
ioDize completely. Some heat is used up for the ionization ofacetic acid. The difference represcnts the enthalpy
of ionlzation of acetic acid.
Q. -11 What is the basic difference between enthalpy of forEation ond enthalpy of reaction ? Ilhrstrflte with
suitnble examples. (N.C.E.R.T.)
Ans. (l) EnlhalPy of formation enthalpy change for the formation of I ltrole ofthe srbstrnce from its elemeltts.
is
For exaDrple, let us colNtder the following two thermochemjcal equatjoDs :
H2 G) +
1
(/1.
02 B) ...- llzO AH. = - mol-l
, 285 8 kJ
(ii) Enthalpy of forrnation is for the formatioD of 1 mole of the substance from its elements only. For example,
we have
CaO (r) + Coz (8) .--_ CaCO3 (t), AH" : - 1?8,'3 kJ mol-l
As 1 nrole of CaCO, (,r) has bcen tbrmed from CaO (i) and COzG) and not fronr iLs elements, aH'is not
enthalpy of fornration. It is simply cr.;rhalpy of reaction.
Why in a reaction enthalpy chlnge is alwnys rvritten per mole even if two or more moles of a reactant or
prodrrct are present in the balanced equation ?
Ans. This is because if the units are multiplied by a number, the unils do not change.
One kg of graphite is burnt in a closed vessel. The same amount o[the same sample is brunt in an open
vessel. Will the heat evolved in the two cases be same ? If not in which case it would be greater ?
Ans. Same in both cases because Ms= 0.
Why standard heat of formation of diamond is not zero thorrgh it is an element ? (H.S.B. 1997)
Ans. The standard state chosen for carbon is graphite and not diamond because graphite is more common and
stabler form of carbon in the standard state.
' r. Is the bond energy of all the four C-H bonds in CHo molecule equal ? If not then why ? How is the C-H -1
bond energt then reported
'
Ans. No because after breaking of C-H bonds one by one, the electronic environments change. The reported value
is the average value of the bond dissociation energies of the four bonds. C-H
The enthalpy change for the reaction N2 G) + 3 Hz(9 .--- 2 NH, (g) is - 92.2kJ. What is the enthalpy of
R
EE
formation of ammonia ?
Aim,l*, rrl **rrg)--_
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o.r.')
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Ans. Hess's law is based upon the fact that enthalpy is a state function r.e. enthalpy change depends only upon the
initialstate (r.e. enthalpyofthe reactants) and thefinal state (re. enthalpyoftheproducts) and does notdepend
upon the path followed.
', Write the standard state for each of the following in which AII/ is taken as zero : Carhon, Sulphur and
Bromine.
Ans. C (graphite), S, (Rhombic) and Br, (/).
r .r, Given that:
O G) + e- + O- - t42kJ nrol-l andO ft') * 2 e- + o'2- G),AH = + 712kJ mol-l
G),AH =
Whatwill be AH for O- (8) + ,- o.2- (g)?
Ans. The second reaction takes place in-two steps as :
O (g) + e- * O- (g), AH = AH1, O-- (C) + e- 02- (g), AH = AH2
-
Hence AHI + AHr= a 112 (/
Q J5 ThesPecilic heot ofa gas is fouDd to bc 0 075 colorie at constant volume oDd its formuls rreight is 40. Whot
is the atomicity ofthe gas ?
Ans. Molar heat capacity. Cu = 0.075 x .10 calorie = 3 cal nrot-l
Co = C, + R = 3 + 2 cal nrol-l - 5 calmol-l
y= Cr/ C,, = 5,/ 3 = 1.66. Hence the gas is monoatomic.
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Q, 1. Under whot conditioh, the heat evolved or f,hsorlred is cqual to the internal energr chnnge ?
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Ans. When the volunte remaiDs coDlaDt
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aDd volumc
are extcnsive but densily (nlass Per uDit volume) and specificvolunte (volume per unit nrlass) are intensive.
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Q. 3. Why we rrsllally study enthalpy change and not internal energy change ?
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Ans. Bccause Dtost of the processes (reactions) are carrjed out iD open vessels r:e. at constant pressure ( 1 irtnt)
=
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thqr-t-#,nerY*?1.Rf;e,?P.i.o-ne,.,cARRvrNG2oi3n'ARKs
Sti il l. What do you undersEnd by open, clced and isolated slstens ? Illustrate with suitable oGmples.
1,, 5l
2. What are exteDsive aod i[tensive proPerties ? Give two examPles of each.
3. Classiry, giving reasor, the following into intensive and exteosive proPerties:
(i) Enropy (ii) Vsclsity (ir'i) Heat caPacity (rv) Surfac€ tension (v) VaPour Pressure
(vi) RefractNe i[dcx
4. How willyou distinguish between the two
(i) open and closed srstem
(r'i) extensive and intensive properties ?
r.,r i-r S. Define Zeroth Law of Thermodynamics. How hasit been useful in the measurement of temPera-
l, < .1 ture ?
\r( 5 5 6, Fxplain, giving reasons, which of the quantities out of internal energy, heat and work are state
r,' S 6 functions and which are not.
7. Derive an expression for tbe work ofexpaDsion ofa gas (le =
-
P A n.
t. (a) Sbow that the Pressure volume work, W =
-PAV
R
(D) List thc imPortaot sign conventions for beat and work.
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9. What do you mean ry hw of conservation of eners/ ? Write a mathematical rolationshiP between
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11. How can you justify that though q and are not state i'unctions, yet (q + w) is a state function ?
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12. Discuss the significaoce of the mathematical expressioo in which the heat absorbed by a system is
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34. Justify the stalemc that 'Sutr b the ultimate source of ener&r.
Scc.5.22. 35. Wbat arc reneerabl€ and non-rcDec.able sources of enerryi Why is there
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a likelihood of cnerry
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cdsis ?
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Lq,*.q., _p,R I.
GARRYTNG s or;o'r uARr(s
Scc.5.l. 1 Define 'thermodynamics,. Briefly describe tho imponance aDd limitistions of therrDodynamics.
Scc.5.2. 2. Define the follo*,ing terms :
(i)s,,ste ropenies (v) Isothermal
Process
Scc 5.-1 3. State ao cs.
to 5.4.
4. Priefly explaio rhe terms btcmar cnerry, work a,,d hcat. How are they iDterrelated ? Justiry that
to 5.6 internal ener$/ is a state funclioo but work and heat are Dot.
5. State aDd explai[ the ,First law of rhcrmodynamics,.
6. Briefly explain the tcnns Enthalpy and Enthalpy change. Ho$, is it related to the internal energy
to 5.E. chaDge ? Derive the relationship.
7' Derilr the reratio$hip between heat of reaction at constant pressure aDd that at constaDt vorume.
Undcr what conditioos are the two equal to each other ?
Scc.5.9. & Pefine
the terms 'specific heat' aDd 'molar heat capacity. Name the tu/o
types of morar heat capacities.
Derive the relationship betweeD tbem.
sc! 510 9. Define 'Energetics'. Frplain with_suitable examples. wbat are the
different modes of transference of
enerry beMeeD the q/$em and tbe surroundings ?
\rc 5I r ' 10. what are horhermic aDd Endothcrmic reacti6ns ? Give three exampres
of each type. Explain the
sign of AH for these readioDs.
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s/s8 l'ralcap's
Scc. 5.1 3. 11. Explain the term 'Enthalpy of Reaction.' What are the factors on which the heat of reaction
depends ?
I
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C
S
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1. Entropy (S) snd cibbs I}ee EnerEr (c). Entop! 6) is a meuwe ofrandon nels of a syitem Tie change
in entroPy during a Process is equal to the heat absorbed isothermally aDd reversibly during a process divided 5y
the absolute temperature ar which heat is absorbed r'.e. N = qi!o. / T.hs units are JK-l mol-1.
/.v.
Gibbs free energy (G) is another lhermod]mamlc quantity related to the enthalpy and entropy ofthe system
according to r.he equation G = H-Ts. The change in irs value during an isothermal process is givin by
AG=AH-TAS. R
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2. SPontaneous process' A Process which can take place by itselfor by initiation indep€Ddent ofrate is called
a sponta[eous proc€ss or a feasible proc€ss. For a process to be spontaoeous, ac is _ve.
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(iii) For an ircthermalProcer,t. AI constaDt tempEratu re, for ideal gas, aE = 0. As alrcady derived iD tbe text
IIT
.. t
Tbtalwork done, w = n CudT = ncuGz - Tr)
|
,t1
- C, or y-t=* -R
or U,,
* - =+
Furlher Cp C, = R. Dividing by ,
- = /- |
,,R (T2 _ T1) -r
Subsliluting this value. wc gel !, =
--r-
Thus if T, > T1, w = +ve ia work is done on the system
If T2< T1, w = ---+e Le. work is donc by the q/stem.
s/s9
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s/60
The enthalpy ol decompsitia of a cdnqwd irto is elcrwru is equal ,o itr e halqy of fomation bu with
opposite sign e.g-,
C(r) + O2G) cozG),aH =- jel skJ R a
-
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I
CO2G) .- C(r) + o2G), AII = + 393 5
'tJ ,!,
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d
f
(r,
o
C
E
S
o,
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I. Isothermal expansion
IL Adiabatic expaDsion
III. Isothermal oompression
Mdiabatic compression.
ie. A(Pl, \/t, Tr)* B (P2, V2, T1)- C (Pr, Vr, Tr)._ D (Pa, Va, T)* A(Pt, Vl, Tl)
It may be noted that the iDternal eners/ change or eDthalpy chan8e or entroPy chanSe in a cyclic proc€ss is
zefo.
t. CoDversion ofhest into !f,ork-C{rtrot heat engiue. The fraction of the heat absorbed by a machine that
is converted into work is called the efticiency of the machiDe. It is Siven by
w Qr- Qr Tz-Tr
1= or=--er-=--r;
where Q, = heat absorbed ftom thc Jource at temP. T2
Ql = heat rejected to the rft,k at temp. Tl
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FIRST LAW OF THEBMODYNAMICS AND CHEMICAL ENERGETICS s/61
path. Clve rc{sorc for yolr onser. if tbe process is carried out at coDstaDt volume or
C
Ans. AH by sccond path will be same as iD thefrstpath is not accompanied by any change in volume ie.
S
because AH is a state fuoction. However, 4 will 6L1 = 4,,. Enihalpy (H) is the enerry storcd in a
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not bc same by second path bec€use it is not a subtanca iE the form of heat. That is why it is also
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Q.3. Whst is tte dltrcrlnc. b.hrcetr hord cD.rBr atrd The changc in its tralue duriDg a proccss ir equal
bond enttolpy ? Explatn takhg exaiDple of to the bcat evolvcd or absorbed if the process is
E2(9. carricd out at or$tant pressure i€. AH = 9r.
AIts. Refer to paSe 5/42. The two are related as H = U + PV or
AH = AU + Ars RT.
Q. J. Vghat is diller€nce between hcst and work ? For
what tJ4,c of proccss€s the two bccome equal ? Thus if a z, = 0, 6g = 61-1.
Ars DlficrEncr betv.€[ hcst 8nd rorlc Refer to page ffAnris +ve ([a np > r,)rntco|E AH > AU.
st9.
It L n s = -ye (Lc. np < nrLG.o@ H < AU .
Condition urder which 4 = r. p1sm 6^, ,.* at
thermodyDamics LE=q+w. Thus q=ry in For rEmple, for the reaction
magnitude when AE = o. Tbis happeos during N2G)+()2G)-2NOG),
the isothermal expanrion of aD idcal gas-
Az, = O, thercfore, AH = AU. For the rcaction
Q. 5. Why teDperature falls during ediabatic expan.
sion of a reol gas but remairs coDsteDt during CH4 ($ + 2 02 @) + CO2 @) + 2 HzO (l)
odiabatic cxlrarslo[ of oD ldcal g&s ?
Az, = 1 - 3 = - 2.:e. therefore, AH < AU.
Ans. In the adiabatic expansion of a real gas, some
work is doDe in overcoming tbe intermolecular For tbc reaction,
forc€s of attraction. This work is done at the CaCo3 (r) * cao (r) + co2 G)
cxp€nse of internal enerry whici therefore falls.
As interoal eDer$r of a gas is a function of
Az, = 1 - 0 - I ie. itis +ve. Henc€AH > AU.
temperaturc, hcoce the tempraturc falls.In case Q. t. Why should thcE he cn.rEr crislE rhcn hr of
ofideal ga6es, the forc€s ofattraction betweeo the conseraatlotr of erelEr hol& 3ood ?
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sl62 l'radec y's Neur Course Chemistrg@
Ans. No dou bt, the law ofconservaaion of eDerg/ holds qglqtjg! St p I. CaLulation of rlondatd entholry
good but theoDly problcm is that the combustion of rcaction
of fuels is a one way process ie. either the M/" = !AH/'(Products) - rAH/o (Reactants)
products of combustion are not mnverted back
into the oriSinal sub6tanc€s at all or they are = I^H/. (o2) + 2 aH/ (HDJ
converted back at a rate much slower thaD the
rate of their consumPtion. For example, coal IAH/." (oF' + (HrO)l
^H/"
burns to from CO2 but CO2 is converted back
= t0 + 2 (- 270)l - l+ 20 + (- 2s0)l kJ m ol-r
into carbon by nature through Photosynthesis at
a much sloryer rate. = - 310 kJ mol-l.
fi. I'lt()BLDMt Step ll. Calculaion of tandord inlemal enetg/
l\,'l'1, ! kW heater take to lroil
How lotgwill s 2 change
2 L of water taken at 25'C ? Given thet the average For the given reaction,
specilic heat of woter in the range 25'C 100'C is - b,nr= (l +2) - (1 + 1) = 1
41E4JK-lg-1.
2 L of water =2000cm3=2000g AH"=AE'+All8RT
(dH2o = lScm ') or AE' = AH" - An, RT
'. Heat required Vy 2 L of water to raise its
temperature from 25'C to
'100'C = (- 310 kJmol-l) - (l)
1) (298
=rnXCxAT (8 .314 x 1o -3 kJ K-l mol- K)
= (2000 8) x (4.184 JK-l g-1) x (100 - 25) K
312 d8 kJ mol-|.
= -
= 62't60o I R
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1
l'tuhl?t,t 4. C.alclulatqtheworkdorewhetr 1l.2Bof
Heat supplied by 2 kW heater = 2000 Js- iron dissolves iD hydrochlortc acld ill (i) s closed vesscl
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H2 gas as
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621(,00 J :
= --'---'-'"1 5lq s Fecl2(4q) + Hz(8)
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= - 5{ 3 kcol mol-l
l'rohlct .l Cnlcttrlat thestandard internnl energy
chaoge for the reoction OF2 (3) + H2O (8) -.
PV=zRr .. v=+
()2 G) + 2 HF G) at 29t K' Slven that the cnthnlpies of o 2 mol x 0 0821 L atm K-l mol-l x 298 K
lormotlon ofOf2 @)' II2O G) and EF G)sre + 20,-250
mol-l =4 89L
and - 270 kJ resPectively'
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FIHST LAW OF THERMODYNAMICS AND CHEMICAL ENEBGETICS 5/63
. . - \n;,;4 = 4.E9 L
AV = VfinEt I)roblen 7. T\c cnthdpy chaDgc lor thc r.{cdoE
I'toh hn
froles (,. lO expardisother-
ofon idcal gas
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We have :
pberlc pr.cssure of 1 0 otm from 320 K to 293 K. During
S
cooli[gr the sample YoluEe decrcased from 274 to 24E aH6;..o. (cacl2) = - 71 52 kJ mol-1
N
(Calculated above)
lor this proceas. For CCI2F2, C, = E0 7 J/(mol K).
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For 2 x l(F kJ of energy, CH1 required Heat produced ftom 8 kg carbon would have been
=ffi-xa =
R 2,67 kl
=ffirz >< 1o6g=3e.55*,
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.'..k emaew = x
As gobar gas coDtains 80% by wcight ofmethane, ffi 1oo = n.r%.
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thcrcfbre gobar gas required x 39.56 kg , ,, ,,,, r. Calculate the work of exporslon when
:
-'-
#
C
tl dtlt.m 2.It an oven, due to iDsumcietrt supply Solutlon. Ele4trolysis of water takes place as
IA
of orygen, 6OVo ol lhe carbon is converbd to carbon- zHzO (t) 2H2@) + o2@)
IIT
=-5065J =1mole=l8g
For rsothermal expansion of ideal gas. AE = 0 so . . For losing 780 kJ of eDerry, water to bo evaporated
lhat11 =-11,=5065J. t8 ,
I = iix780E=3les
This heat is used uP to heat mole of water.
Applying thc relation , ' ,- The shndord enthrlpy ofcomhustion
q=mxcxLT at 25'C ot hydrogen, cyclohexene (C6llr0) and
5065=18x41tl4xAT cyclohexone (c6Hr2) ore snd
-241, -31100 -3920
or N =6125 kl/mol respectively C$lculate the heat of hldrogenn-
'. FinaltemPerature tion oIcyclohexere.
R
(I.LT. 1989,I.S.M. Dhonbod 1992 ; Bihot C.E.E. 2003)
EE
=zO"C+6725=26'125'C
An intimate mixture of ferric oxide, .Solution. We are Siven
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t
lerO3, and aluminium, Al,ls used in solid fuel rockets' (i)Hz+ iO2 .- H2O,aH =-241 kJ
C
Crlculate the fuel vrltre Per Bram End fuel value per cc.
!_7
-*
S
ofthe mixture. Heats offormatioE and densities ar€ as (ii) c6H to + 02 6co2 + 5H2o
; .
N
follows :-
IA
AH = kJ
aIrT(Alz Or) = 399 kcaVmol -3800
IIT
Total
qH8 G) + HzG) qH6 G) + cH4 G),
_ (3.62 +r) litres
C
ot 5 x Eqn. (i)
N
.'. 1 litre of the ntixture willcontain qH4 + 3 x Eqo. (rv) gives the required result.
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C1Hl0 required to get the same czlorific value as @1*t, (9 * ! o, G) Hzo (D,
,Sq!-uqo!!" Energ/ available for muscular work I'rot'lu lJ EstiDatethe average S-F bond cner-
S/ tn SFa. The standsrd heat of formatiotr Yal cs of
C
)\
kJ mol -l S G) and F @) are :- 1100, 275 rnd E0 kJ
= fib. x 28t0 SF6 k),
S
N
I
mol - rcspcctively. (r.I.T. teee)
IA
= 720 kJ mol-l
Solutiop. We are Siven
IIT
(c) Neither state functiori nor path fuDction (o\ (l l(liamond) + 2Hr(g)- CHIG)
(d) Both srate function as well as path function :. agraphire) + zurgl-''''''- cHa (t)
The relarionship between enrhalpy aod internal (()C(graphirc) + 2Il2@)- CH1@)
enersr ciange is
(a)AE=^H+P Av (b)AH = +p
(d) C (graphite) + 4H+ CHa (g) tt.r..t: Ies2t
(c) d,H=-aE-P (d)PAV=^EdE+ ^v 9.'fhe enthalpi of vaporizrtion of liquid water using
^v ^I{
When a reaction is carried out in a clGed vessel the data
(a) qp < q" (b) qo , q"
ari6;l * lorgl Hzo (D ;
(c) qp = q, (d) q" = o.
- 6H = kJlmole
Thc boDd energies of H-H atrd Cl-{l are 430 kJ -285.'17
mol-l and Z2kJ mol-1 Nlrfor HCI
respectively.
tt, ts1 * lorg) Hzo E) ;
mol-|. The bond enerEr ofHcl wilt be
R -
AH = - 241 .84 kJ/mole
EE
i6 91 kJ is
4n kl
(a) (b) us Lt !.1+43.93kJlmot (6) - 43.93 k]lmot
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ture (T) is
KOH and 0.5M H2SO1 soturions, respecrivefy,
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lq--1 .43 (b) + 3.'12 at 293 K, lhe enlropy change at rhat iemperature
-3 72
(c) (d)+7.43. tr.t1: tse| (a) can be negative but numerically larger than
xt2gScalK-l
l.a
/3S
2.b 7.o &c 9.o
ll, .t l0.d
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,. j-.r. ,.r,,r,'i Neut Course Chcmistrglfift[fi
call be negalive, but numerically smaller than coe)+ro2@)-coz@)?
x / 2gB c2lK-r
(d) aH =
(c) cannot be negative
(a) AH < ^E
AE
(d) cannot be positive. (1.'i,tl t)1 ,' ! i
(c) AH > AE
13. of CO2 G), CO G), N2O E) and No2 GI) in (d) AH is independent of the Physical state of the
^H'r
.lrfaH ^H
=
^E
equalto +2RT (d) aH = Ae +RT.
(c)AH =
C
does
(c) the sum of standard molar enthalpies of for-
(4) nuclear eners/
IA
-\dfeDerg
of $a.Jitational pull. )t)ttt) tr)l.rt\
23. Which of the following reactions is endothermic ?
(z,rtrrcity of water in equ ilibriu m wit h ice
\-Ny'lvlolat heat ..-znc)
- at constant pressure $ JdtrI2 + o,
(a) zerc (b)Hz + Clz- zHCl
(b) innnity (c) HrSOo + 2 NaOH Na2SO 4 + 2 HxO
(c) 40 45 kJ K- mol-lI -
(d) None of these. 6.EM.C. 2000)
(d) 75 48 JK-r mol-l. Q.l.T 1997 24. Amount of heat required to change 1 g ic€ at 0"C
to 1 I steam at 100'C is
17' ln thc reaction: s + 3202' so3 + 2x kcal
(a) 616 cal (D) 12 kcal
and soz + 1 / 2or- so' + / kcal' the heat of
(c) 7 71 cal (d) noDe of these.
formation of S02 is
IHl4aM'"IlET 2000)
(r -
(D) r) 25. The Arr/' for co2 (,:), co G) and H2O G) are
@{1zr - v1. and - 241 't kJ mol-l rcsPec-
i(ll\l l'tl I it'') -393
5,
- IlO 5
tivetv. The sulndard enthalpy change (in kJ) for the
lt. At constant T and R which one of the following reaition cor lg; + H2 G) co G) + H2o (g) is
statements is correct for the reactiol
-
RS
r2. b 13. c 14. c 15' d 16. b 71. d 18. 19. d 2O. b,cd 21. a
2r. d 23. a 24. c '
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FIRST LAW OF THERMODYNAMICS AND CHEI\,IICAL ENEFGETICS
5171
(a) 5u 1 qdu.z (a) + 172.5 lbt'-lto.s
(c) 262.s (.1)- 41.2. tl.I.T 2t)t)0t
- (c)
-1070
(d) --476.s
26. ID thermodynaDrics, a process is called reversible (e) + I10.5
when A',:ruh L L la 2t)01 :.i I li.ti ti 200.t)
(a)surrouDdings and sysrenr chango into each
32, Crmpounds wirh high heat of formatioo are less
othcr
stabic because
(b) there is no boundary bcrween system aDd sur-
(a) it is difficult to synrhesize rhem
roundiDgs
(l)/enerry rich srare leads ro insrabiliry
(r41iie surrouniJings are atwa,s in equitibrium with
the systenr (c) high temperature is requrred tosynthesize them
(d) the system changes into th() surrouDdirigs spon- (d) molecules ofsuch compounds are distorted
(aneously l.l.l. )tilt I
'.r0lWhich one of the tbllowing sraremcnts is false ? The heat required to raise the EDp€rature of a
J?lfork is a srate funcrion body by t K is calted
(6) lbDrperature is a state function (4) specific hear lbfihem,at CziBcity
(c) Chalge in the slate is completely defined when (c) water equivalent (d) molar heat capacity
the initial xnd final statcs are sp€cified \1.1.L.8.ti.2002)
(d) Work appears at lhe boundary of rhe system.
Io a reaction irrvoMng or y solids and liqu ids, whictl
ii: ) t)t: I ofthe follotPiDg is true ?
2t. Change in eDthalpy for the reacuon (4) dH < AE lpftu - tn
2H2O2(l)- (c) aH > AE (r/).\rr = At. r r{f
2H2O (l) + 02 G) R .^
EE
if hear of lbrmariotr of H2O2 (4 and H2O (/) arc
35. C (diamord) ...* C (graphire), AH = _vc. This
AR
-188
kJ mol-l and kJ mol-l respectively,
-286 shows that
C
ls
_/
| J3}craphire is more stable than diamoDd
S
./7 fo', s
t.a 29.b 32. b 33. 34. b
'
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N e.4
(a) a0 0 (b) 42 3 C-H linkage$ are 350, 600, 400 aDd 410 kJ per
mole respeclively. The hcat of hydrogenation of
(c) aa 0 ethylene is
(d) not defiDed because pressure is llot constant ,,,
(r) - mol-l
n)\ 1') - t?o kl nlol ' 260 kJ
/,/' (c) - 400 kJ mol-1 (d) - 4s0 kJ mol-l
f *li"t ot,l" follovinB reaction define (^.r.8.|i.|i.2003\
(a) C16;amo,a) + ()2 (q) .... Co2 G)
47, One gram otsamPle of NH4NO3 $ deconlposed iD
(c)
N
(d) Enthalpy remains unchanged 60. 1 nrolc of H"SO4 is ntixed with 2 otoles of NaOH.
S
3kr
IA
Internal energy is
(a)57 @)2x57 3kJ
IIT
,t).
60.
!
h
sr.
61.
.
e
52.a '..1 *
62. b
ro1
n'
, 56, d 57, a 5t. d 59. c
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5174
HIN
4.
rl r 'l
el = l+.430+i zl12
L-
or B.E (l ICI) = (215 + '-21191 100 cal
= 245 kJ
at ffc
AG=AH -TAS or AH =AG+ATS i00"c.
6. Sec solved exanrPlc on Page 5/31
(,) CuSOa (r) + dq. -* CUSO{ (./4),
AII - -
15 89 kcal 2s, AH'Rcacrion = [^l]i(co) + ^Hi(l]2o)l
(li) Cu506 .51'1rO + aq.- Cusoa (a{),
AH=+280kcal
F4n (r)-Eq. (ri) direclly gives the rcquired rcsult
1'.
R
^- -t7-- -1{=-',1 AHi(or]
L}l't(ll"o
EE
2tl. allR.ac(ion = +
-.c 12
aH - aE =An8R1' -z Atri(Hzoz)
AR
tha[ 50 nll and hence heat evolved is less. 0)--(li) gives rhe requirccl eqn. ie for the Siven
11. It will be less than -t because ac€ttc ilcid ls a $eak reaction, AII = r- - -v
acid but cxact vrlue cannol be Preclictecl. ,\s AII = - !e,l < ,l'
aG .aH -TAs- - r - 296 x As For ac Lt)be J0' for deconrposilion of I mol H'zo (13 g) heat re-
as can be negatiu. rrrt as ,norroi"-r"t','ir,ii
-ve,
x/298 quired =2 x 142 5kJ =285 kl
Eqn. (i)+ Eqn. (,,) gives tbe required rcsult (ij) Co (s) + ! orlsy- co, (sy,
6H=-2E3kJ
15. Aln:c{37)+ o2G)_.co2€) AH"= ! 1
('()' all
of Ainr: cQ9) +io2Lc)-- ( ()
= l
This N sanre as nrolar enthalpy of combustion
graphite. F-qn. (i)-Eqn. (ri) giYes the rcquircd result
Cp=- AV =0'
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FIFTST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS slz5
Graphrte will have lower energy and hence Breatgr ,16. Ainr i CHz = CH2 + Hz .. CII3 - CH3
stability-
}IHIIH
36. As (ontirner ii' ch)scd ilnd lnsuldlaJ. lhc nrocess
acliabatic so that 0. /\\
is t!t
ll L C ltrH ll 'tI-C- -ll
11 =
^F =.1 +W. Atj:W+0 ,\ ,l
37. Ibr l1(llaLratlc expansron, q= 0. AHreacr,oi :: B.E (Reaclants) -: B.E (Products)
36. l0 n'rlof 0 5M NaOH = 20 x 0 5 :[BE (4c-H)+BE (C = C) + B.E. (H H)
= 10 millinloles -lB.E (6c-rr)+BE (c - c)l
= milliequivalcnls
10 = B-E. (c = c) + B.E. (H - H)
100mlofo 1MHCI =100x0l -28.8 (C - r{) - B.B. (c - C)
=600+400-2x110 350 kJ
= 1000 - 1170 = - 170 kJ.
Heat cvolved trorD deoomposition of 1g
=123x612kJ
= 100-r U
la =123x6.12x80kJ
AIJn"o. = - 100r kJ
= 602 kJ.
39. 5tl0 nrl of 2 N HCI = 1000 nrl of I N HCI
4E. C8Hr8 + +C}2....-ACO2 -I H2O
250 ml of ,l N NaOH = 1000 ml oi I N NaOH
. B)' dcfinition, heat cvolved
Ar{'R*"ti.; = Is + e aH/ (H2o)l
='t kJ
R ^H/'(co2)
- l^H/(c8Hr8, r -f aH/ro2)l
EE
40. I]=I-I+PV
AR
- z Il,L. (Products)
= (433 + 192) * 2 (364) = - 103 kJ,
g). Work done =-P".,rAV =-3(6-4)Latnr
not diamond
= - 6 I-arm = - 6 x 101.32 J = - 608 J.
42, L\ ng= np - nt= 1' 6 -- - 3 51. aH =A(E +PV)- AE + A(RT) = r\E + RAT
Grrphilc * Dian'rond
56. 5(t cru3 ofo 2NHzSOl
45,
Afl.",uion = AII/ ((lian]oDd) - AH/(Braphite) = 50 x 0.2 \{eq = 10 \{eq
: 1.t196 - 0 23 = 1 666kJlnlol(). 50 cnr3 of t N KOH = 50 x t N{eq = s0 Mcq
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5n6
'llus t0 Mcq oI H2SOI will neulralize 10 Meq of 59. EqD. (it) + EqD. (rii) givcs the required result.
KOH 60. I nrole ofH2SO4 = 2I eq. of H2SO4.
slo3oJJ 1
.'. He t tiberared = , lu 61, For nronoatomrc gas E =
t RT
= 0 573 kJ = 573.,. It=E+PV=E+R1'
WhcD fI2O (g) chaDges to H2O (/) i / coDdcDsc- 15
rron rakes nlacc. heal isrvohcdi.,' Allz rs grciiler
=|n'r +nr =]nr mor-l
than all I. 62. H Ractior = t B-E, (Reactants)
58. 169 Ctll pro(lucc beat = 890 kJ - E B.E- (Products)
. 3 2g CII4 will produce hcat c) + a B.E. (c - H) + B.E. (l{ - H)l
= IB.E. (c =
- (c - c) + 6 B.B. (c - H)l
[B.E.
=lix3.2=l78kJ =[45 +4 x98 +103] -{80+6x981 = - 28 kcal.
ADDITIONAL UESTIONS
As ee rlio n- Re a s o n Ty p e Q.u esii ons
The questions glvcr b€low coDsist of an 'Assertlon' i! col umn I snd the'Reaaon' ln column 2. Use the folloui ng
key to chooce the appropriate onsroer. R
EE
(a) Ifboth ssscrtlotr and reason are CORRECT and reason ls the CORR.ECT cxplanatlon ofthe assertion
(r) If both assertion ard resson ore CORRECT but reason is not the CORR.ECT cxplanatloE of the assertion.
AR
(e)
IA
AssertioD
IIT
1. Thc value of enthalpy of neutralization of a weak A]l the OH- ions furDished ty I g equivalent of a strong
acid and a strong base is numerically less thaD 57 1
base are not completely ncutralized by the H3O+ ions
kJ.
from the weak acid.
2. Standard enthalpy of graphite is lower than that ol Standard enthalpy of elements is taken to be zero ar-
diamood. bitrarily.
3. Enthalpy ofcombustion is negative. CoDlbustion reactioD can be exothermic or endothernric.
4. Ahsolute value of H canDot be deteflDined. Absolute value of E caunot be determined.
5. Endothermic compounds are more stable than the Endothermic reactions have positive eDthalpy of fornra-
cxothernric compounds. 1ioD.
6. Enthalpy ofvaporisatioD is alwa)B endothermis water is an exothermic compouod.
7. Enthalpy of neulralizatiou is always exolhermic- Neutralization involves reaction between an acid and a
hase.
& Enthalpy of neutralizatioD for both HNO, arrd HCI NaOII is a strong electrollte. (A.r.r.M.s. t997)
with NaOH is 57 1 kJ pe r mole.
True/Falee Staaemente
luhich of the following stalemenl$ arc not trTte ? 2. An extensii€ property depends upoD the anrouDt
Rewrite them cor7e c tly. of the substance.
l. An isolated q,stem is tha t which cao exchange ener- 3, In an isothennal procEss, tempcrature remains con-
ry but not Datter with the surrouDdings. slanl beaause ro heal caD enter or leaw the slatem.
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FIRST LAW OF THERMODYNAMICS AND CHEMICAL ENERGETICS 5177
The work doDe on the slstem is positive whereas Enthalpy of combustion is the amouDt ofheat evofued
the heat absorbed by the system is positive. when the oulnber o[ n]oles rls representcd by the
balaDced equation have been completely oddized.
IDtemal eDer$/ change is the heat chaDge at con-
stant volume whereas the enthalpy chaDge is the 12. The total amount ofheat evolved or absorbed in a
heat change at constaot Pressure. reaction depcnds upon lhe Dun]ber of step.s in
lnternal eners/ is a state function but eothalPy is which lhe rcaction rakes placc.
not a slate functioD. 13. The e[thalpy ofcombustion ofcarbon (graphitc) is
7. The standard state ofa substance is 0'C and 1 atm nor equal to that ofcarbon (diamond)
pressute. l.l. Enthaltry ofsolution is alwars positive.
The totalamount ofheat cvolved or absorb€d io a
15.
E. The S.I. unit of hcat is'calorie'.
reactioo depeDds upon the number of step6 in
9. The absolute value of intemal enersr of a sub- which the rectioD takes place.
stance cannot be determined. 16. The enthalpy of mmbustion of carboD (graphite) is
10. W is positive when tbe aork is done on the system. not equalto that ofcarboD (diamond).
The ditference belween molar heal capacityat coD- 15. AHsubtima(ion = ..-. + ..-.
staot pressure aDd that at constant volume for oDe
C
7.
39 8 of beDzene will be ...-
IA
(o) A B
1. System can sxchanBe botb matter and eDerry with the surroundiogs. 1. Closed slstem
2. System can exchange neither matter nor ener$/ with the surroundings. 2. OpeD E6tem
3. Systcm can q(change eners/ with the surroundiogs but oot matter. 3. lsolared slstem
4. S,,stem can cxchange matter with the surrou[diDgs but not eoer!ry. 4. No such systgm exists.
(b) A B
1. A proc€ss which is carried out infiDitesimaly sloA,ty. I Isochoric proc€ss.
2. A process is carried out such that temperature remails constant. Isobaric process.
3, A process in which Do heat cnters or leaves the q6tem. 3. Isothermal process.
4. A process io which the volume is kept coDstant. 4. Re!'ersible proc€ss.
5. A process io which presure is kept coDstant. 5. Adiabatic process-
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5178 Pradct: St's Ne@ aourse Cltemistrqffiill
15. AHgoslqn, Mvaporisation 16. 1632 kJ l7.'fossil. lE. endothermic 19. less, ionization.
Ty?e Q.uegtions
5.
8.
R
EE
AR
C
S
N
IA
IIT
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UN[]F
Cllernical Donding
and lvl olect)lar SErucb.)re
i
i ;ri
t:
:', i ,i:i ii
ia ':; 'U,
:---,
';--1 ,! ,'i:i' i,,
Atoms are usually not capable of free exist- forward from "-e to time. These are :
C
elements exisl" as one species e.g. 2. Yalence Shell Electron Pair Repulsion
N
(VSEPR) theory
IIT
6tr
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612 Neu/ Conrse Clrer istrq
they combine chemically with any other element 6.4. Lewis Symbols :.:i:+:::i:':ri.:ii:r::i::::::-"'-::ri:.r:':i:::ir:',:rr:;:i::i::i:i::'
nor among themselves. Their electronic configura- In the formation of a molecule, only the outer
tions are as follows : shell electrons are involved and they are known as
Noble gos Atomic No. Electronic valence electrons."fhe inner shell electrons are well
Confrguration protected and are generally not involved in the
Helium 2 2 combination process. It is, therefore, quite
Neon 10 2,8 reasonable to consider the outer shell electrons i.e.,
valence shell electrons while discussing chemical
Argon 18 2,8,8
bonds.
Krypton X 2, 8, 18, 8
G.N. Lewis introduced simple symbols to
Xenon 54 2, 8, 18, 18, 8 denote tle valence shell electrons irl an atom. The
Radon 86 2,8, 18,32, 18,8 outer shell electrons are shown as dots surrounding
the symbol of the atom. These symbols are known
From the study oI electronic configurations as Lcwis symbols or electron dot symbols. These
of thc noble gases, it is clear that thcy are chemi- symbols ignore the inner shell electrons. A few
cally inactivc because they havc 8 electrons in examples are given below :
thcir outermost orbit except in case of helium
which has 2. Hence, it was sttggcsted that they .Li .Be.B. .C.:N.:O
possess stable electronic configurations. In case
:F: :Ne:
o[ all other elements, the number of electrons in
their outermost shell is less than 8 and hence they Signlticance of Iaris symbols. The number
are chemically reactive. This led to the following of dots arouad the symbol gives the number of
R
electrons present in the outermost shell' This num-
EE
conclusion:
ber of electrons helps to calculate the common
AR
The cloms of ddferent elemcn* combine with valency of the elment. That is why these electroLs
cach other in order to complzte their respective are called vqlence shell elecions -
C
arc>4)
ri: tlL"! .lo Aio|l]s Cclllr,l.,i i
r i.lories r,;f Ci,,.micrl Llnrnbin::tiL-i'll
For example, Li, Be, B and C have valencies
to the number
1, 2, 3, and 4 respectively i.e. equal
As discussed above, atoms combine together of dots whereas valencies of N, O, F and Ne are 3,
in order to complete their respective octets so as to 2, 1 and 0 respectively i.e. 8 minus the number of
acquire the stable inert gas configuration. This can dots.
occur in two ways : Nowwe shall discuss each type ofbond one by
of one or ntore one.
,( By complete tralslercnce
qnolhet.This :' r : '
process is 6.5. Elecirovalent or lonic Bond
:. '. : : ' :r
elecions from one atom to
'. :1 '
..".:'.:.:.": "
.' '.:: .
Iosing an electron, an atom becomes positively (2) Formation of calcium fluoride. If cal-
charged since now the number of protons cium (atomic No : 20, electronic configuration :
exceeds
the number of electrons. 2, 8, 8,2) loses two electrons, it is converted into
A+ A+ + e,- calcium ion and attains the stable inert electronic
arrangement of argon. On the other hand, fluorine
(atomic.No. : 9, electroni-c conf,rguration : ;,7)
"
b comesnegative- on gaining one electron forms fluoride ion and
ly charged. acquires the stable confrguration ofneon.
B*e-+B- Here, calcium atom loses two electrons and
The oppositely charged particles formed of postive charge
forrn-s calcium ion with two units
above attract each other by electrostatic forces of and the two electrons are transferred to two
attraction. The bond thus formed is known as fluorine atoms, which are converted into fluoride
elecfiovqlent or ionic bond. ions, each with one unit charge. These oppositely
Such a type of bond is formed only when one of charge.d ions are then held together by strong
the atoms can easily lose electrons while the other can electrostatic forces of attraction.
gain electrons and thus each acquires the stable
electronic arrangement of the nearest noble gas. -
Examples
(1) Formation of sodium chloride. Sodium
[,i']
(atomic number : 11) has electronic configuration I cu l'*
2, 8, 1. By losing one electron of its outermost shell,
it acquires the inert gas configuration of neon and lz,a,s I
changes into ion.
Na- Na+ + e-
R [,i,]_
EE
2,8,1, 2,8 2,8
AR
this
IA
(2,8 7)
Now we have rwo species, one is positively
(2 8,8)
Mc:l:i : _+ t yt l'. [,:i']'-
charged sodium ion and the other is negatively 2,8,2
charged chloride ion. As soon as they approacL
2.6 2.8
each other, they are held together by strong or MgO
electrostatic forces of attraction. Thus, formation
of sodium chloride takes place. (2) Formation of magnesium bromide from
magnesium and bromine.
[Na+l +
[, :: r
] -....-, tN"l*
[, :f
t]-
. Sr:
Ihe above steps may be represented directly
L'?:'l
as fbllows :
Naj,/-\"
]'.
+ .Clt Na+ :Cl:-
F
-
f_
(3) Formation ofcalcium sulphide. (ii) the formation of a negative ion hy gain of
electrons from another kind oI atom.
(,li) holding thc Positivc and ncgative ions by
cr:---S .. ! ....- Caz+ frl :s:.],- orcos electrostatic forces o[ attraction.
288
(2,8,8,2) (2.8, r) The formation of ionic bond depends upon
2'8'8 the following factors :
(4) Formation of sodium sulPhide. (i) Ionlsation Enthalpy (lonization Ener5/).
Mg (g)
ln the
itivcly
d ions
A" + B-_......-A-B-
negatiye ions is very common, e.g, in case of
chlorioe, electron affinityis + 3zlti H/mole i.e., ..'1f4 energ, relcased when ItE rcqaisile nutnber tt!
gnsitive snd negoliye ions ambine to form orc molc
Cl @) + e-.- Cl- + 3zE kJ/mote ofthe ion 'compound is calhtl lufrice energ.
or E.A. : + 3rt8 U mol-l
Hence, the halogerrs can form negative ions of latticc cncrgv o[ the
easily. On the other hand, elements ofgroup 16 form
ihe greator u,ill be tlrc
divalent ncgative ion-s (by gaining two elections) but nd hencc grc.rtcr uill he
not so ea-sily. This Ls becarxe the semnd electron
iLffrnity in case of these elements is much lcss and is Ws know that the force of attraction bctwccn
negative ,.e., energy Ls required to form divalent ions. ths oppositely charged ions is dircctly proportion-
Let us discuss the case of orygen. Fifst, oxygen will al to the magnitudc of the charges (q,,qr) antl
add up one electron to lorm monovaletrt ion which is inversely proportional to thc square o[ the tlis-
accomparried by release ofcertain amouot of energy. tancc (r/) betrvcen thcm. 1.c.,
But in tle process of addition of second electron io iltxq)
the monovalent oxygen io4 energ5r is required to Force of attraction cf, ---------)
overcome the forcc olrepulsion exerted by the nega-
d:
tively charged monovalent ion to the incoming
Hencc the value o[ lirttice encrgy dopcrrtls
clectron.
oG)+e- ...-o-(c), R
upon the follorving rwo l:crors I
EE
(a) Charge on the ions. Thc highcr thc charrc
EA' : 1 142 ;t' -o'-'
AR
+ 142_693
=- 551 kJ mol-l. altlrcti0n rvill hc lcss
while in case of small ions, intcrnuclcrr rlislancc is
less and so lbrce of attraction is (rcrrtcr.
directly) and hence for predicting the stability of series of steps indirectly may be represented by a
the ionic compound formed (h"cause Lrger.is the cyclic process as under :
negative t,alue for lattice energy' greater is the , al{'r
stiUitity of tbe compound formed)' The method is Na (s) + )wtr(g) -.------* NaCl(s)
known as Born-Haber cycle' It is briefly described
below taking the example of NaCl (s). +SJ *1o l
The heat of formation of NaCl (s) is found to Nu G) cl(s)
be -411kJ mol-l i.e.
+r.E. J/ -E.A.T
+ lclr($ --.*
1
Na (s) NaCl (s),
t
Nr+ G) cl- G)
----1-----_--J
AHi=-411kJmol-l
We canimagine that one mole of NaCl (s) can
be prepared by the following series of steps :
Applying Hess's law (according to which the
(i) Crystalline sodium metal is sublimed to
heat chinge is same whefher one mole of thc com-
form gaseous atoms
pound is formed directly or indirectly through a
Na (s)---'-* Na (8), number of steps), and using the ;ymbols withottt
AH=AHsoblimation:S proper signs, we have
(ii) One-half mole of gaseous Cl, molecules is 1
AHi=S+7D+I'E'+E'A'+U
dissociated to form 1 mole of gaseous atoms
Substituting the values with proper sigrtr (posi-
R
tive sign if energy is absorbecl and negative sign if
EE
1
cl
i.rrg) - (8),
enetg1 is relased), we get for the case of NaC!
AR
lix \Ill'l.li. Calculote the lattice enthalpy of Ionizqtiort enargt of Mg : * 2IE7 kJ mol-1
Vupotisarion energt oJ'Br, (/) : + 3I kJ tnol-
|
MgBrr. Given that
Entlrulpy of formarion of MgBr, : - 524 kJ tttol-l Dissociation energt oJ' Bt, G) : + 193 k! mol-
|
-a--u
?:,ft;;@lft, h E M,',9,,F,-,O,,Ri i
1. Calculate the lattice enthalpy of KCl. Given that gainof 1 mol of F (g) is kJ mot-l and (v)
AHsub of K = * 89 kJ mol-l, AHDi.r. for 1 mole -333
AHifor LiF (r) is 1 kJ n:ot-r. (N.C.E.R.T.)
-594.
of Cl, = + ?A.4 kJ n:ol-l, AHionization for K ft') =
[,\n' -1011 6 kI mol-l]
+ 425 kI mol-1, AHetectron gain for C| G) =
-35S R
3. Calculate the lattice enthalpy of CaCl,, given that
EE
kJ mo[-l, aH7 (KCl) = --438 kJ mol-l. the enthalpy of (i) sublimarion of Ca is
121 U mol-l (i) dissociation ol Cl, ro Cl is
AR
[.\rrs. kI mol-11
-719 242.8kJ mot-l lirl; ionizarion of Ca to Ca2+ is
2. Calculate the lattice enthalpy of Lil given that the
C
enthalpy of (i) sublimation of Li is 155.2 kJ 2422kJ nrol-l 1iv; elecrron gain fbr Cl ro Cl- is
S
N
-795 kJ mol-1.
(N.C.E.R.T.) [ \ns kJ mol-l]
-2tt70.tt
HiiilN,T$ FOR DIFFICULT ?R.OE-LEMs
7. * jo + I.E. + E.A. + U 2. v =^Hi- . ], + r.r. + e.a.]
^H"t=s [.
- 438 :w*! (244) + 4zs---3ss + u = -594. 1-(155 .2 + 75.3 + 520-333)
= -1011 .6 kJ mol-l
or lJ = J19 kJ nrol-l 3. U : - 795 - + 242.8 + 2422 - 2 x 355]
ll2l
= -2870.8 kJ nrol-l
R
EE
AR
1 variflble electrovalelcy. [o case of transistion n]etals, certain atoms cnn lose difl'ereDt numbr ofelectroDs
N
1o
acquire stable configuration. I lence they show variable electrovalency. For example, Fe forms Fe2+ and Fe3+
IA
a
IIT
ions and Cu forms Cu+ and Cuz+ ions. The more stable ioD is the one which has nrore stable core r.e. lhs
confiSuration obtained alter the loss of valence elcctroDs. For example. Fe3+ salts are ntorc stable than
Fe2+ strlts
26Fe = 2,8,14,2
or H-N-H
N
,/=-).':\
IA
H
(6) Formation of Metbane (CHa) molecule
H.+.C. +.H
I
H_C_H
H-cr
".-r.glr-@or +
I
H
Multiple covalent bonds. In the examples
c;ted above, each atom contributes one electron. H
Hence the coyalency ofchlorine and hydrogen is
1. The bond formed is called single coval€nt bond
(7) Formation ofEthylene (CrHn) molecule
and is representedby single line ( ) between the
- H.+ +.H
two atoms. Covalent bond may also be formed by
the contribution of two or three electrons by
:c::c: .---.....'
Bond Pairs and Lone Pairs. The shared In this structure, duplet of H is complete but
pairs of electrons present between the atoms are octets of C and N are not complete. Hence multiple
called bond paris because they are responsible bonding is required between C and N. Octets of C
for the bonding between thc atoms. On the other and N will be complete if there Ls triple bond be-
hand, the valence electrons not in-volved in bond- tween C and N. Thus we have
ing'(i.a., sliaring) [re'shdWn as such and are
called non-6onilig-g €I-ecJrons or lone pairs or
uilshaieil p:airs. H:C::N or H-C=N
5.10. Lewis Representation of Simple , l'.li {\11'l ,1r 2. Tb drsw the Lewis dot structure
Molecules and lons (the Lewis StructL!res) i:::::i of CO!- ion.
As e4plained later in reaction 6.13, Lewis Step 1. Total number of valence
structures have a number of limitations, yet they are electrons of CO, : 4 + 3 x 6 : 22
helpful in understanding the formation and proper- (oC :
2,4, BO :2,6)
ties of moleculs to a greater extent. Hence writing
of Lewis dot structures of molecules and ions is very Step 2. Total number of electrons to be dis-
useful. These structures can be written through the tributedinco3- : 22 + 2 : 24
following steps : Step 3. The skeletal structure of CO, is
Step 1. Calculate the total number of valence
electrons of the atoms present.
o
Step 2. If the species is an anion, add number oco
of electrons equal to the units of - ve charge and if Step 4. Putting one shared pair of electrons
R
EE
the speciesis a cation, subtractnumber of electrons between each C and O and completing the octets
equal to the units of + ve charge. This gives the total of orygen, we have
AR
Step 5. Complete the structure by repre- (ii) To dntw the Lewis struchlre of CN- ion
senting the unshared electrons (U = A S).
Stepl.A :
EXAMPLES. (, fo draw Lewis sttucture of CO, 1 x 4(forC) + 1 x 5(forN) + 1
(for negative charge) : 10 electrons.
Stepl.A = 1x 4(forC) + 2 x 6(forO)
Step2.N = I x 8 (forC) + 1 x 8(forN)
=4+12=16electrons. : 16 electrons.
Step2.N = t x 8(forC) + 2 x 8 (forO)
St€p3.S = N-A = 16 - 10 = 6 electrons
= 8 + 16 = 24 electrons.
St€p3.S = N - A = 24 - 16 =8electrons (shared).
Step 4. Drawing skeletalstructure with shared
(shared). .
parrs
Stcp 4. Drawing skeletal structure with
shared pairs C::N-
o:: c:: o Steps. U = A - S = I0 - 6=4
Step5.U:A-S=16-8=8.
. . Complete Lewis structure will he .'. Complete Lewi-s structure will be : C !! f.f i
'l Lewis structures of some typical molecules
:O=C=O: and ions are given in the Thble 6.1 below :
:C=O:
S
N
IA
IIT
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Nerl Course Cheruistrg
(Nitro'rs acid)
o
.. -o,.
,/fuii)(Niric acid)
HNor H:O N H-4-Nz'/
,//
o 'o:
o II :iLH
O:H
..t..
H-O-P-O-H
(o) H3PO1
(Phosphoric acid)
H:O or
.'t..
:o:
:
o-=N-ii:
(r) No:- o
I o
t..
S
(Nitrate ion)
N
IA
: '9'
IIT
o
(,0 sol-
(Sulphatc ior)
o s o
ol- o t'z- ot
(Peroidc ion)
t,g
I l+
(xre) HrO* i; ll
. (Hydrcnium ion) l"' H
t
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CHEMICAL BONDING ANO MOLECULAH STRUCTURE 6/13
n: o: cr: o:
C
.\J.
Ii\,L\IPLI1 Cahulate fomal chatge on each
IA
|
O-atom of Ot mokcule.
IIT
nor-ul.Uu.g. on Cl = 7 - 0 - j tSi = *:
Solution. Lewis structure of O, is as follows :
,,\ ----6
t--
i, Solution. (i) Lewis structure of CO3- ion is
=6_4_r(4)=o
Formal charge on central O-atom numbered 2
I
=6_2_;(6)=+t Formal chargs on C atom
Formal charge on end O-atom numbered 3
I =4-o-i<rl=o
=6-6-j(z)=-t Formal charge on double bonded O atom
Hence ue represent O, alongwith formal
charges as follows ;
=6-4-lrol=n
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6114 Pra tt r t: yt's Neut Co urse Chem i strgt lfrfil
Formal charge on single bonded O atom
1 : CI: ," t ! (Be has 4 electrons arouncl it)
=6-6-)(z):-t d]
CI:
F:
ao aa
Formal charge on single bonded O atom F:
3Cl;:Cl:
=6_6_|Q>=_' ( 10 e around P)
( L2 e- around S )
R
EE
The main advantage of the calculation of for-
mal charges is that it helps to select the most stable
:F
AR
structure i.e. the one with least energy out of the :F: F:
C
onthe at9m,s. .r
IA
:l11s:_.
IIT
( 14 e- around I )
Although octet rule is able to explain
the formation of a large number of com- Again the octet rule is violated in thesc
pounds, there are some exceptions to this molecules.
rule as follows : (iv) Formation of compounds of noble
-/(iY' Formation of compounds involving gases. Noble gases which have already completed
hydiogen. As hydrogen atom has only one shell octets (or duplet in case of helium) should not
containing one electron, it needs one more electron form compounds. However, their compounds
to complete its shell i. e. to acquire the nearest noble like XeFr, XeF' XeF5, KrF, etc. have been ac-
gas configuraf,ion of helium. Hence hydrogen needs tuallv prepared.
to complete its duplet and not octet, as e:rplained (v) Odd electron bonds/Odd electron
in the examples above.
molecules. There are some molecules and ions
(rr) Formation of comPounds like in which the bonded atoms contain odd number
BeO2 , BF3 , Atcls etc.In each of these molecules, of electrons (usually 3) between them. Thc
the central atom (Be, B or Al) has less than 8 bonds thus present are called odd electron
electrons i.e. these are electron deficient com- bonds and the molecules are called odd
pounds as shown below : electron ftrolecules. Some common examples
are given below :
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CHEMICAL BONDING AND MOLECULAH STRUCTUBE 6/15
together in the molecules like Hr, Cl, etc. in which The 'partial overlap' means that a part of the
there are no ions and hence thers are no electros- electron cloud of each of the two half-filled atomic
C
tatic lorces of attractioni.e. it could not explain the orbitals becomes common. As a result, the prob-
S
(ii) It could not explain the shapcs o[ overlap is much more than at other places. Thus,
7
IIT
molecules containing covalent bonds. the two electrons (with opposite spins) although
keep on exchanging position between the two
(iil) It could not explain the release of cnergy
atoms but are present for maximum time in the
during the formation of a covalent bond.
region of overlap and hence are attracted to both
To explain the above limitations, lwu impor- the nuclei simultaneously thereby forming a bond
tant theories called modern theories of covalent between thg two atoms.
bond formation have been put forward. Thcse are
based on quqntum nrcchonical pirtciples. -fhesc fhe strength of the bond depends upon the
arc :
extetrt of overlapping. Greater the overlapping,
stronger is the bond formed.
(1) Valence Bond (VB) theory
To understand the concept more clearly,let us
(2) Molecular Orbital (MO) theor), consider the following examples :
In the next section, we shall takc up a brief (i) Formation of Hydrogen Molecule :
discussion olValence Bond theoryonly and that too When two hydrogen atoms having electrons
in a simple manner without entering into the math- with opposite spins come close to each other,
ematical complexity involved. The discussion of their s-orbitals overlap with each other result-
Molccular Orbital theory will be takcn up at t-2 ing in the union of two atoms to form a
level molecule (Fig.6.1).
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6/ 16 tlur dr r 7.'s Neut Course Chemistrgffi[l)
fluorine baving an electron of opposite spin in ?,
orbital, the half-filled orbitals overlap each other
resulting in the formation of a fluorine molecule as
shown in Fig. 6.3.
''?.ffifJ 'iB..ffiEiI'
''Lt,,-}''i " -)-i'
lg.ATOMtC 1s-ATOMtC OVERLAPPINGTAKES
oRBrrAL oBBrrAL tL6ft5
F.ATOM F,ATOM
""8.t#hEtst
FIGI.JRE 6,1. Fornntion oI hydrogen molecule.
formed between the two atoms. Ttis is shown in H2, IIF and F2. As the orbitals involved in the over-
Fig.6.2
C
rTheirbond strengths are in the order F-F < fI-11 < II-F
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CHEMICAL BONOING AND MOLECULAR STRUCTUBE
6117
thes
lhes
gy of the system.
ITE DISTANC E
IN FIN
' NO INTERACT|oN -
cot\,tE
. CLOSER
.. INTERACTION
. STARTS Ile+l. I do= BoND LENGTH
E = BoND ENERGY
o o
FTGURE-6.4. (a) No interactions at large distances
+ff
(b) lnteractions start a< atoms im. closr,. lr,
I
l< --r
R
EE
t>
AR
UJ
F
t!
C
POINT OF
S
N
IA
In
a certain
amourt to breat
the bon
have to
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Ne.4 CouYse Chen istY4
6/18
i
o
(l
l.tl
ztrJ
F
zul
F
o
0-
INTERNUCLEAR DISTANCE' d+
R
FIGURE 6.8. Variation of potential energy
EE
whnn t,," hnlium .toms are_ brought closer'
AR
6.15. fypes ol C
siqly .,,I1 :':trr- i-: '
C
S
. thc
He\ ler'
ATOM (A)r\ th4
R
EE
2pz ORBTTAL 2pz OBBTTAL p-p OVEBLAPP|NG MOLECULAR
oF F-AroM oF F Aror.4
*,"
AR
, ,r.*frt"ort?* .;nZTE:tL
C
along the internuclear a"ris as representeU in fig. fi'.i2. ' p_p orbitals
@ O>€ D@€
s-s OVERLAP s-p OVERLAP p.p OVEBLAP
X
+
I
I I py
Pr Px
Fig. 6.16.
N.ATOM N-ATOiI
N2 MOLECULE
1t
R (N=N)
EE
1l
FIGURE 6.14. p-p overlapplng forming a pi bond
AR
A z-bond is seldom formed between atoms FtGuRE 6.15. Formation o, nitogen mol€cule'
C
carbon d
N
two
IA
R
EE
AR
C
S
N
IA
IIT
!/3,:::.T:9^:l:i:T
slmmetncal aboul 9ronry ore eredron croud,
the intemuclear axis.
rotation about a o_boDd is p6sible.
+
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Pradeep's','61!:gl',:', il;:. 'iii WID
6122
b. tt:l.
',.-;i
mean positions.
,A
four C- H bonds in CH4) do not possess lhe same
bond energy (due to change in chemica_l environ_
ment), _therefore bond energies are usually the
average values.
The bond encrgies o[ some common boncls
have been given in Tablc -5.I ot Unir -5.
Fattors allecting bond energr
(i) Size of the ato,ns. Greatel the size of the
atoms, grealer.is the bond length and less is the Molecule: H-H O:O N=N C=O
Dond drssoctatron energy i.e. less is tbc bond
strength.
Bond order: 1 Z 3 3
(i,
Multiplicity of bonds. For thc bond be_ . For odd electron moleculos, as thc three
elcctron bond is considerecl as
tween the same two atoms, greater is fhe multi_ to hill
covalent bond, bond order can be"quivalent
fractional also.
plicity of the bond, greater is the bond dissociation
energy. This is fustly because atoms come closer
and secondly, the number of bonds to be broken is
For example, Lewis structure of NO is : N I O:
more. (See page b,l5). Hence its bond or,lcr = 2 ].
(iiil Nunber of lone ?uirs uI L.lectrons pru:jent.
2
^
Greatcr (he number o[ lone pairs of eiectrons it is interesting to observe that isoelcctronic
. R
species have the same bond order e.g.
EE
present oD the_bonded aloms, greater is the repul_
sroo bctwecn thc utoms and hence less is thc bond (i) F, and Ol- have 18lectrons each and each
AR
dissociation r:nergy. For examplc for a few single of them has a bond order = 1.
C
l-one pairs
Furthcr, it is also observed that
IA
ofelectrons 1 0 I 2 3
.,-(i) Greater the bond ordcr, grearcr is the
IIT
on cflch atom
I stability ofthe bond rla greater is the B'ontl enthalpy.
ll(,hd ehcr$/ ] tJ8 Ir,3 I{r, lly Grcatcr the bond orrlcr,
fkJ nol ') .bond.(fi)
length.
shorter is thc
(3) Boud Angle. We know that a bond
11lll:1 ",e,,:.rii.r .. .
is
lbrmcd by lhe overlap uf atomic orbitals. Tbe direc- .-.
trrrn rrl overlap gives the direction of the bond.
The tnglz baween thc lirr6 rvFresenting thz direc-
lions of he bonds i.e. l,he otbitals contairrinE th2
bonding electrons Lt caltcd tlw bond anfu.
II isexpressed in degrees, minutes and It ionisation
):...""9: 19. exampte, H _C H bond angtc in
energy o atoms in
ClH4, H N- H bond angle in NU., H il _ their is
- - H
Proper
advity is a
bond angle iu HrO and F- B-F bond angle in
BF, are shown belorv :
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Pradcc y's
6124
+6 -6
H- cl
of reprtscnt.rtive (lcmcnls
S
TAIILE 6.4.
N
GROUP
t3 t4 15 16 11
IIT
H
2.20
(3.06)
Be B C N o F
Li 3.U 392
098 1 .51 2.04 255 304
(1 83) (2.6',1) (3.08) (3.22) (4.43)
(1 28) (1.e8)
si P s cl
Na Mg AT
3 16
0.93 I .31 1 .61 1 .90 219 2.58
(2.3e) (2.6s) (3.s4)
(1 21) (1 63) (1 .3?) (2 03)
Ga C,e As Se Br
K Ca
255 2.96
o.82 100 1.81 201 2.18
(1 30) (l .34) (1.e5) (2.26) (2 sl) (3 21)
(1.03)
In Sn Sb Te I
Rb Sr
196 2.05 2. 10 266
0.82 095 1.18
(1.83) (2.06) (2.34) (2 88)
(0.ee) (1 21) (1.30)
Ba TI Pb Bi
CJ
2.33 2.02
0.79
Values without the brackes are on Paulin8 scale
Values in brackcts are on MullikeD's s€le'
scale -noD-evalualive
rMathematical calculation ot elerlrolleBalrvity bascd on MuUikcn
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CHEMICAL BONDING AND I\,4CLECULAB STRUCTURE
6125
How electrone{ativity is difrercnt from
electroE afliniry ?
H 3 Cli or
l
R
EE
I
MORE +d -6
ATTRACTED H_cl
AR
H:H
l
I
EXACTLY IN H-H
THE CENTRE
:I 9j: ot
FIGURE 6.1a. Non-polar covalenr
bond between H-atoms.
t
MOBE ATTRACTEO
TOWARDS CI
metrical and there is no charge separation at all.
-The examples of some non_polar molecules FIGURE 6.20. Polar covalent bond in ICl.
are Cl, ,
O, , N, etc. Examples of some other molecules containing
more than one polar bond are shown in Fig. 6.21.
+
H
of
ll
r case ofBFr, the
resultatrt of two bond moments' being equal rmd y:J
opposite to that of the third, cancels out'
-'
6 charactcr would be
: 6'12x 10-18esu'cm
-6lZD
ltottcwca =l 03 D (Given)
'. Eo ionic chatactet
il,
ll = 'r"b.'rnrd, t*
It R ltionic
EE
= 1'9: *^
-itz too = t6'837o
AR
C
H*o cl '
IA
-
FIGLBE 5.25. Dipole moments of zero ,or symmelrical n)olv )e' io ic charactcr oJ lhe molecttlc'
Solution' If the molc ctic wcre 100'%
Applications of Dipole Moment : ionic,
lt ion;" =4xd
- (1 602 x 10-1e c) x (1 596 x 10-10,7r)
-- 2 557 Y. 10-2e Cm
llot'"n't = I 964 x 10-2e Cm (Givcn)
"u"
non-polar molecules. = 76.E1%.
?p.f1'f;1|El$},E; R
45 D aDd i(s boDd lenpth is 1 654 A late the
The obscrved diPolc momcnt for a molecule AB is 1
percrnage of ionic character in the bo;: @ihart E c'E' 20N) rs 3%I
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CHEMICAL BONDING AND MOLECULAH STRUCTURE
6129
5.'Meltlngand Boiling Points. Covalent com- The main points of difference between
podnds have low melting and boiling points be- electrovalent and covalent ocrnpounds are
C
'1. * .]i,
_- :1: jr.:
(r'r) These conlpounds may be solids or liquids or gases.
(ii) Thcy are Dtadc up of nrolecules held together by
$'cak van der Wa.rl,s lbrces of attraction.
(r) They have generally low melting aDd boilitlg poinrs.
(v)
(u)
(r'ii)
0rr'i)
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Nerl Course Chent istrtl
6/30
.(i\Todistingtishhetweencisarullransiramerr..Ihisisbascdonthcfacllhalcisison]crusuilllvhushighcr
dipole mome nl than lrans-isom€r '' g'
n-" I _cl
'-a-t' il 1, 2-Dichloroethene (+- shows
,-8.o
O) +
cis (,L
C)IC \H
trans ('r = 0)
directioD of diPole moment)
onho, meta and para itomers' This is based on the fact that the dipole nloment of
lii) To dislinguish between
p-iiomer = 0 and thal of ortho is Sreater than lhal ol meta e & R
EE
CI CI LI
lcl -t
ol
AR
Q., + Dichlorobenzene
C
S
ortho- CI
p=148D
N
P=2 54D
Par'a-
IA
IIT
Theory Shell
6.23. Valence Shell Electrcn Palr Bespulslon
This
$ un- t940
able e lust esPie
simp in the
I
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CHEMICAL BONDING AND MOLECULAR STRUCTURE 6/31
in 1957. The basic conccpt of this theory is as (5) The exact shape of the molecule depends
follows : upon the total number of electron pairs present
The central atom is linlted to other atoms by around the central atom.
covalent bonds which are formed by sharing of Based on VSEPR theory, the shapes of
electrons. Thus, the central atom is surrounded by molecules containirg 2, 3, 4, 5 or 6 electron pairs
shared pairs (or bond pairs) of electrons and there around the central atom, all of which may be bond
may be some lone pairs o[ electroDs also present pairs only or some of these may be bond pairs and
(which have not taken part in the formation of the remaining may be lone pairs are given in Thble
bonds). The stabililv ofthe molecule demands that 6.6 on next page alongwith examples of each type.
it should have minimum energy. I[ the electron The detailed discussion of the examples is given in
pairs surrouading the central atom are nearer, they section 6.25.
will repel eachother, therebyincreasing the energy 6.24. Hybridisation (Valence Bond Approach) :,i:,,i:
of the molecule. But if the electron pairs are far
apart, the repulsions between them will be less and No doubt VSEPR theory is able to€dplaiAth;e
so the energy of the molecule will be low. Thus the shapes of simple molecules but is unable to predict
main idea of the VSEPR theory is as under qaEx. Moreover -
:
_..1&E-efasf shape u-a_!C!Sbe.-9f
talking o[ the direclioa of electron pairs does nol
Tlu elaron pain noarding thc centrul lbm -G"6-o U" u..y ,"tional. lt was onlywith the advent
repel ow atwther aad move so far aparc lmm one
anolher hd there ore nolwther repulsitm between
'of Valence liond Theory that the shapes of
molecules could be explained more preclsely. As
tham. As a raull, thc moleculz
and ruximum stability.
already explained, according to Valence Bond
thcory, a covalent bond is formed by the overlap of
R
Since after repulsions between them, the half-filled atomic orbitals. The direction of overlap
EE
electron pairs take up definite positions around the gives the direction of the bond. However in apply-
AR
central atom, hence the molecule has a dehnite ing this theory, a diffrculty was faced in a number of
s'hdpe or geometry. cases as explain below :
C
The above coricept leads to the following As a covalent bond is formed by the overlap
S
therefore the
IA
VSEPR thcory) which help to hnd the shape of a covalency of the element should be equal to the
IIT
TABLE 6.6. Shapes (Gcometry) ofmolecules containing bond palrs onlyor bond paim and lone pairs.
2 0 g=.=g
3e
Lincar a,.L
il
I
3 3 0 u
JY .l: :I
R
EE
Triangular planar
Triangular planar
AR
C
S
N
IA
/\
IIT
: o: ,9,
l 4 0
Tetrahcdml
3 1
Trigonal prramidal
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6/33
CHEMICAL BONDING AND MOLECUI.AR STRUCTURE
TABLE CONTINUED
') 2
PCls
-5 0
5
Tligonal biPt'rar:liclal
R
Trigonal biPYramidal
EE
sztd
AR
C
S
sFn
l
N
4
IA
IIT
J 2
ctF3
XeF,
2 3
(,
Linear
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6134 Neut Couyse Chem istrr!
TABLE CONTINUEO
6 0 SFu
L
sfd
Octahedral
--t
sL'
d1
5 1 clF5
R
EE
AR
C
Square pyramidal
S
N
IA
IIT
,-* ldi''
<)rt L_
4 2 XeFa
l'o
lt.,'
Square planar
x
Note. In predicting geometry of molecules containing double bond, the double bondis considered
as one electron pair. For example, in case of ozone, its two resonating structures are
'9-o=o -- 6=6-o,
In each structure, the central on" to* pui' two bond pairs (counting double bond
as one bond pair), n"o"" it rru, t"Xttof,l# "oa
"
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6/35
CHEMICAL BONDING AND MOLECULAR STRUCTURE
BeF2, boron has a covalencyof thrce as in BF, snall lobe opposite to a big lobe on the other side
of four, e.g, in as shown in Fig. 6.26.
whcreas carbon has a covalency
CHo, CClo, CO, etc.
To overcome the above problem, it was sug-
g OR
a
SIMPLY
e
case of carbon. Its atomic numbcr is 6 and so its
eonfiguration in the ground state Ls FIGURE 6.25. Representation oI a hybrid orbital
Thus now carbon has four unpaired electrons (i) Only those orbitals which have ap-
thereby explaining tetravalent nature of carbon. Its proximately equal energies and belong to thc samc
one s and three p orbitals can overlap with the R
atom or ion can undergo hybridisation
EE
half-filled orbitals of reactiug atoms, formiug four
(ii) Number of hybrid orbitals produccd is
covalent boods. But covalent bond formed by 2s
AR
three bonds formed by 2p orbitals should be at 90' should participate in hybridisation. Even completc-
IIT
o.
sp2 HYBBtDtsA.rtoN
Gsb
TWO sp HYB R lD OBB ITALS
rnae i sf Hvsnro onituLs
FIGURE 5.27' Diagonal or sp hybridization
FIGURE 6.2a. Trigonal or sp2 hybridization
Each ol thc hybrid orbitals formcd has 5017"
.r-charactcr arr.J 50'h 1t- chaructcr' Thc rcmaining (ii1 All compounds of carbon conl aininr.
trr,, p-rrrhilirls rvhich Jrr nrrl particil'atr: irr C-Ctioublchond.
hvbriclisation remain as such. ll thcse arc hull- Thcsc arc discussetl latcr undcr 'Shalrcs r,l
lillccl, thcy nray lorm bonds with othcr atoms having mol, curcs.
R
EE
hall-llllcd atomic orbitals. -1. Tetrahetlral or sp3 hybridisation.
,/daupr,gs. A tcw compounds in rvhich.y.,
AR
(r) All compounds of beryllium likc BcFr, ncw equivalenl orbilalt, the lypc oI hyhridisation
S
b itu L\.
C=C triplc hond Iike acetylene (CrHr).
Thcsc rvill be discussed later under 'Shapcs of
Thcsc arc clircctocl trrrvards the lirrtr corncrs
rnolccttles'. ol a regutar tctruhedrctn and mlkc an anqle ol l09'
lS' u,i(h one uno[hcr as rcltrcsentcd in Fig 6 29
2. Trigonat or sp2 hybridisati(,n.
One 2s and two !p orbitals undergo sp2 hybridisation to form three haH-fill9d sP2-hybrid orbitals
which are planar and oiiented at an angle oi Lz}'to each other. These overlap with half-frlled orbitals of
three fluorine atoms to form BF, whic6, therefore, has triangular planar shape as shown in Fig.6.31.
sp2HYBRlD ORBITALS
It shares these electrons with three fluorine atoms CHo as represented in Fig. 6.32' Thus CHn is a
S
i.e. its Lewis structure is tetrahedral molecule with each H-C- H angle
N
,f
IIT
,
(D) On the basis of VSEPR theory. Ceutral
atom in CHn is C. It has four valence electrons
F B: F:
vrhich are shared with four hydrogen atoms. Thus
there are four bond pairs of electrons present
Thus B atom is surrounded by three bond
around the central atom (carbon) as follows :
pairs which according to VSEPR theory take up
positions at irn angle of 120'with respect to each
other thereby giving it a triangular planar shape as tI
shown in Fig. 6.31. H:C:H
(3) Shape of Methane (CH) molecule:
H
(c) On the basis of hYbridisation.
Atomicnumber of C:6 Now according to VSEPR theory, these four
Its electronic configuration in the ground electron pairs will repel each other and thus move
state is kz bz 2p'rU', so far apart that there are no further repulsions
between them. The only shape possible is
The electronic configuration in the excited tetrahedral as shown inFig.6.32.
state is lsz bl zprrzpiui Some other examples of molecules/ions
One 2s and three 2p orbitals undergo sp3 having tetrahedral shapes are CCla, SiF4, SiH4,
hybridisation to form four sp3 hybrid orbitals which NHo+, BQ- etc.
aie arranged tetrahedrally nt il1 angls of 109" 28'
to each other.
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CHEMICAL BONDING AND MOLECULAR STRUCTURE 6/39
HH
H-AfoM
(i) C-C bond length : 154 pm (5) Shape ofEthylene (C2H.) molecule : The
(ii) Each C-H bond length : 110 pm electronic configuration of C-atom in the excited
state is : uC : b2 2sl U:zp'r 2?:
(ii) Each H-C-C
In the formation- o[ ethyleoe molecule, each
or H-C-H bond angle = 109'28' C-atom undergoes spz hybridisation, thus leaving
ooe ?p, orbital in the original state, i.e., in the
(iv) C-C bond dissociatiotr etrergy
unhybridised state. The three{p2 bybrid orbitals of
: 3,18 kI mol-r. each C-atom are planar and are inclined to each
other at an angle o[ 120'. One spz hybrid orbital of
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6140 Neqt Coutse Chemistrq
the first C-atom ovorlaps with one spz hybrid undergoes sp hybridisation leaving two 4, orbitals
orbital ofthe second C-atom along the internuclear in the original unhybridised state. The two sp
axis thereby forming one sigma bood between hybrid orbitals of each C-atom are linear, i.e., they
them. The other two spz hybrid orbitals of each are 180' apart. One sp hybrid of the frrst C-atom
C-atom ove ap with the half-filled tu-orbitals of overlaps with one sp hgbid orbital of tbe second
H-atoms along their respective iaternuclear axis
C-atom along the internuclear a:ris thus forming o
forming o-bonds. The unhybridised !p, orbitat oI
bond bctwecn them (Fig. 6.35). Thc second sp
the first C-atom undergoes sideways overlappiag hybrid orbital of each C- atom overlaps with the
with the unhybridised 2p, orbital of the second half-hlled 1s-orbital of H-atom again along the in-
C-atom, thereby forming az bond between the two ternuclear a.:ris and thus forming o bonds,
C-atoms. So the formation of ethylene molecule
may be represented as shovm in Fig. 6.34. The un-hybridised 2p, orbital of the hrst C-
atom undergoes sideways overlapping with
the ?, orbital of the second C-atom, there-
by forming a z bond between the two C-
atoms. Similarly, the unhybridised fu.
orbitals overlap sideways forming another
z bond between the two C-atoms. Thus all
the carbon and hydrogen atoms are linear
and there is electron cloud above aadbelow,
in the front aad at theback ofthe C- C axis.
R In other words, there is electron cloud all
around the internuclear axis thus giving a
EE
6.35.
C
,r-€o
S
N D
N
IA
IIT
(i) C :
C bond length = 134 pm
(ii) Each C-H bond length = 199 Oot 1l
(iii) Each C-C-H or H-C-C bond angles g-6lIE6-s
L
= 120"
(rv) Total C = C bond dissociation energy = FIGUBE 6.35. Formation of acetvlene (CeH.r)
614 kJ mol-r. molerr.rle (cylindrical shaf e).
Out of 614 kI, the bond dissociation energy
for obond is 3tB kJ (as alreadymentioned). There-
The various bond paramcters of acetylene
molecule are as follows
fore, the bond dissociatioa energy for z bond is :
614- 3.18 : 6kJlmole. Hence z bond is a weaker (i) C = Cbond length = 120 pm
bond. This is the reason for high reactivity of com- (i/) C-H bond length = 108 pm
pounds containing z bonds. ( ) H-C-C bond angle - 180'
(6) Shape of Acetylene (C2H2) molecule : In (iv) Total C=C bond dissociation encrgy
the formation of acetfene molecule, each C-atom :811 kI mol-1
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CHEMICAL BONOING AND MOLECULAH STRUCTURE 6141
(7) Shape of PF, molecule. In PFr, the that axial P-F bonds are slightly longer than
cenl.ral atom, phosphorus, has the ground stale P- F bonds (Bond
equatorial lengths : P- F axiatl
e lecrronic configur;ton lsz 2s2 2p6 atz qt,q) y! = L58 pm, P-F equatorial : 153 pm). However
NMR (Nuclear Magnetic Resonaoce) studies show
One of the 3 electron gets promoted to 3d orbital
that all the hve F atom-s are equivalent and can
giving the electronic conhguration 'ts2 2sz 2p6
exchange their positions* and hence all the five
kt 3p:3pjp: Ut. Thus it involves spJd hybridisa-
tion (rig. 3.ro).
P
- F bonds have the same length. The reason for
the difference in the two studies is on account r,i the
fact that electron diffraction gives instantaneous
F
picture of the molecule whereas NMR takes time
more than the time required for the interchange of
ixial and equatorial F atoms.
Otherexamples. Similar geometry is expected
for PCl, and SbCl, molecules. However in PClr,
axial P-Cl bonds (bond length : 219 pm) are
longer than equatorial P-Cl bonds (bond length
= 204 pm).
(E) Shape of sulphur hexalluoride (SF)' In
EouAloRtAL SF5, the central atom, sulphur, has the ground state
electronic confguration G 2;2 2p6 k2 3p13p1y3pt,
FIGURE 6.36. Trigonal bipyramiCal geometry of PF5 and F has 1"'2.? 2pizpiU:. One of the 3s
R
elecrtrons as well as 3p electron get promoted to 3d
EE
Alteflrutiveb,, the central P-atom has 5 valcncc orbitals giving Ge electronic configuration
AR
pairs of electrons.
the ralence shell. As a result, the c€ntral atom is
S
.q
F .. 'i
:S:+6 .F: + F ..5 F:
According to VSEPR theory, for PF, to have
minimum energy, the bond pairs of electrons
i:"f .. F:
should be as far apart as possible from each other.
This is possible only if the molecule acquires a According to VSEPR theory, for SFu to have
trigonal bipyramidal shape. minimum enerry, the bond pairs of electrons
In this structure, three of the fluorine atoms should be as far apart as possible from each other.
lie in the same plane as phosphorus atom and are called ThLs is possible only if the molecule acquires a
equatorial fluorine atoms and the bonds formed are rtgular octahedral geometry (Fig. 6.37).
e led equatorial bonds, The other two fluorine atoms IfSFu, four S are in the same plane
lie at right angle to the plane of equatorial bonds and -Fbonds
are known :s axial fluorine atoms and the bonds at right angles to one another and are directed
formed by them are called axial bonds. towards the four corners of a square. The oth€r two
F atoms lie at right atrgle above and below the plane
Bond lengths anil Bond angles in PFr.
of F atoms.
Electron diffraction studies of PF, gas show that
SFu molecule is a symmetrical molecule and,
the equatorial bonds are at angle of 120" with each
other whereas axialbonds make an angle of 90'with therefore, is stable and far less reactive.
the equatorial bonds. Further, these studies show
?Thc interchange o[ axial and equatorial po6itions is called'pseudorotation'.
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6142 Pradeer's Nett Coursc Chemisrg JIIDT
Its electronic configuration is
4 ts, N, zpt, 21, zlt"
,'i One 2s and three Q orbitals undergo qp3
hybridisation formiag four sp3 hybrid orbitals out
of which three contain one electron each and take
,,;\ part in bond formation and the fourth rp3 hybrid
,'i Y orbital contains a lone pair of electrors and hence
cannot participate itr the bond formation. The four
F Z--v .1p3 hybrid orbitals will obviously be directed
towards the corners ofa tetrahedron and hence the
bond angle between any two sp3 hybrid grbitals
would be 109' 28'. Now, when the three spr hybrid
orbitals, each containing one electron only, overlap
FIGIJRE 6.37. Octahedral geomety oI SF5. with the ls-orbitals of H-atoms to form NHr, the
expected H-N-H bond angle is 109' 28'. But ex-
Otherexamples. TeF 6 is also expected tohave
perimentally, the bond angle in NH, is found to be
a regular octehedral geometry.
107'. The obvious reason for the decrease in angle
B. SHAPES OF MOLECULES CONTAIN. is that the lone pair repels the bond pairs. Thus the
ING BOND PAIRS AS WELL AS LONE PAIRS formation of NH, molecule may be represented
(9) Shape of Ammonia (NHr) molecule :
diagrammatically as shown in Fig. 6.38.
Atomic number of N : 7 R
EE
1s
AR
7N =
@
C
S
N
N
IA
IIT
BONDING
sp3.HYBRID ORBITALS
OR
HH
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CHEMICAL BONDING AND MOLECULAR STAUCTURE 6143
Such a shape is known as trigonal (or hian- angle is t09'28' . But e4perimentally the bond angle
gularl pyramid in which thE three H-atoms form isfound to be 104. 5". The reason for the still lesser
the triangular base of the pyramid with N-atom at bond angle inH2O thaninNH, is that in thi5 snss
the apex. The same applies to molecules like there are two lone pairs of electrons present which
PCl3, NF3 and HrO+. repel the bond pairs. Thus in this case the repul-
(10) Shape of water (HrO) molecule : The sions are more than those in the case of NH,
shape of HrO molecule can be explained exactly in molecule. The formation of HrO molecule maybe
the same way as in case of NH, molecule. represented as shown in Fig. 6.39. Thus water is
Y-shaped or bent molecule.
Atomic number of Orygen : 8
HF molecule is linear since it has only two
Its electronic configuration is
atoms though in this case also, four electron pairs
1s2N2fi2p)zpr, (one bond pair and three lone pairs) form
One 2s and three p orbitals undergo sp3 tetrahedral geometry.
hybridisation forming four sp3 hybrid orbitals out Some other examples of molecules/ions
of which two contain one electron each and the having shape similar to thatof HrO are SOr, FrO,
other two contain a pair of electrons (i.e., lone- NH, , SCI etc.
pair) each. As usual, the four sp3 hybrid orbitals
thus formed are directed towards the corners of a (11) Shape of SF. molecule. This is an ex-
tetrahedron and hence the bond ang.le between any ample of a molecule in which the effect of lone pair
two sp3 hybrid orbitals would be 109"28'. Now when has a great significance in deciding the shape of the
the two sp3 hybrid orbitals containing one electron molecule.
each, overlap with the half-filled fu orbitals of RAtomicnumber of the central atom (S) : 16.
EE
H-atoms to form HrO, the e4pected H-O-Hbond Its electronic configuration is
AR
C
go=
S
N
IA
IIT
BONDING
sf-HYBRID oRBITALS
LONE PAIRS
OF ELECTRONS
R
EE
AR
FF
Lone pair occupying Lone pair occupyhg
C
Due to smaller size and high electronegativity 6.26. Co-ordinate or Dative Bond t:::rrlij:iil::i;i,:i::!:i::i:ii;iii:::::::ir:::
107.5'93.4" 91.5' 9t.2' Trm itt thz lottulhn oI d hond, fu ewftrn ,air
(b,e pair) b doaodry ortcdk,i bd *Edb! botk
Conclusion. In similar molaub, as the lhE atoE,J fr ai lo @r,pki ilun odztg tlu botd
elearorugutivily of lhc ccrrtdlatom decre$, und
tlu she innerses,lhe borul anfu dffr?uff$'
[ord it ald u*rdilutc hotil or dative botd
Thus whereas in case ofcovalency, the shared
Elfect of electronegativity oI the surrounding pair of electrons has equal contribution from both
atom on the bond angle of similar molecules. For the combiningatoms, inthis case shared pair comes
example, in the trihalides of phosphorus (all of from only one atom, and this atom is termed as
which have pyramidal shape), thc bond angles in- donor and the other atom tus acceptor. This bond is
crccse as follows : R
represented by an arrow pointing from the donor
EE
PFt PCl3 PBT, PI, to thc acceptor. Compounds havingthis linkage are
AR
This is evidently due to the fact that due to ii semi-polarbond or co.ionic bond. Some illustra-
S
high electronegativity off,, bond pair ofelectrons is tions are given below
N
:
more attracted towards F i.e. it lies away from the
(i) Combination of Ammonia and Boron tri-
IA
AICI, etc.
Similarly, CH4, CCl4, NH4+ etc. all have the same HF
bond angle viz. 1@?8'.
u +H-N+B-F
tt
(ii) Bond angles may vary due to cqtain other
factors also e.g bond angle of NH, is greater than lt
HF
that of NF, but bond angle of PH, is less than that
FIGURE 5,43, Formation of a co-ordinate
of PF, (See Page 6/67). hond between NH3 and BF3
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i rrtlrt,t,'s Nett Couvse Chemistrqlftfi[fi
(ii) Sulphur Dioxide : Sulphur as well as orygen atorns have six valence electrons and each is short
of two electrrons to complete its octet. In order to comPlete their octets, sulPhur atom and orygen atom,
share two electrons each thus forming a double bond berween them. Sulphur atom still has four unshared
electrons, i.e., two lone pairs to donate. Thus sulphur donates one lone pair to one orygen atom, forming
a co-ordiuate bond between sulphur and orygen and a molecule ofsulphur dioxide. By accepting this lone
pair, octet of oxygen is also completed, as represented in Fig. 6.44.
J,.
FIGUBE 5.44. Formation oI sulphur dioxide molecule
(iii) Ammonium ion : In NHr, N atom has ooe lone pair of electrons. It can donate this lonc pair to
H+ ion thus forming a co-ordinate bond as represented in Fig.6.45.
H
H
(ii
H:N: +H+
w H
H
)r-! [":
H
R
EE
FIGURE 6.45. Formation of ammonium (NHfl ion.
AR
:
S
N
IA
:o:
IIT
H:O:S: O: H
X/ :o;
.o
CO-ORDINATE BOND
FORMED HERE
LONE PAIRS
EMPry
NH" MOLECULE
s-ORBITAL
OF H+ ION
NH ION
.o"'--
EMPTY
FIGUBE 6.45. Formation of NH{ion (orbital concept)' s-oR BITAL
OF H+ ION
H3O tON
(ii) Formation ofhydrotrium (H3O+) ion'As
already explained under the shape of HrO 5.47. Formation of H3O+ ion (odital concept)'
FIGLRE
molecule, the O-atom in HrO still contaios two
d hybrid orbitals, each containing a lone pair of
R
EE
The dipole moment of ,CO molecule is greater than expected This is because
of the presenc€ of a dative
i
AR
(co-ordinate) bond.
C
I H2O2 mol€cule is said to have an open- book t)?€ structure as shown iD the Fi8' below
:
S
N
l\-r,'
IA
95 pm
- o-o-
IIT
G= 2.1 o)
,l47.5 pm
ir:: 3. The abi.t ryof the bybrid orbitals to overlap is in theorder tt:E.:lj" gcater is theP- character, Sreater
is tbe ability to overlaP.
iii:i a. The bond an8lcs formed by different hybrid orbita.ls are in the order rP (180) >sp2112/|--1','f lfm
Slie
ttle bond augle.
8re€Er tbc J{haracler, Sleater is
The n -bond formed betwecn S aDd O atoms in SO2 molecule is due to overlaP betwecn thet P-orbihlr
or
i :ii 5 .
betwee[ p orbital of O-atom with d{rbital of S- atom (calledPz - d,r bonding)
p\rZ pt,
fis = 7 s2 z!2 2P6 3 t2 Z fiZ p,r-P,r
(Ground state configuration) b bonding
= 1 s2 2 s2 2 P6 3 tt 3 P1, 3 P)3 Pl, 3 d\
(Ercited srate confiSuration)
8o=1s2|sx2rtzP1y2Ptz
S-atom undergoes,rpz hybridlsation leaving one half-
Iilled 3pz orbitaland ooe d-orbitaluotrybridized. Out
of tro half-fllled orbitals of O€torn, oDe is invoh/ed in
formatioD of d-bond with S-atom and the other in
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6/4A
6.27. R
o-
,,.,.,/ \ \\
..-./ \
'P
"9' ,
This representation is somewhat mldeading be-
cause it suggests that the molecule has two forns, I
ard tr which oscillate back and forth between them.
One can arrive at a better representation of
the hybrid slructure by superimposing one struc-
For example, the structure of ozone can be
ture upon the other.
The result of this superimposition is shown
below :
ii
.'i ...-
:9 ..o..
oB
/"t,
where each orygen atom has an octet of
electrons. But this structure is unsatisfactory be-
cause it depicts the central O atom to be bonded
This representation indicates that (!) there is
to one O atom by a double bond and the other O R
one stable hytrid form, (rt) this form is symmetrical,
EE
atom by a single bond. Since double boud is
shorter than single bond, the two bond lengths in
(iii) the same length
(inb
AR
length : 121pm). But experimental evidence not mediate befween the two resonating structures
S
N
only shows that the bond lengths are equal but drawn earlier.
IA
also shows that the bonds are intermediate be- Thus the structure of O, molecule may be
IIT
tween single and double bonds (equal to 128 pm). written a,s
Hence for molecule like Or, a single Lewis struc-
ture is unable lo explain the observed facts.
Hence an alternate Lewis structure can be writ-
ten in which the double and single bonds are ,/o\
interchangcd. ,/\
.../
..o.. \\...o.
6... oR
,/'\
Neither of the above two structures can ex-
plain all the properties of Or. Hence the actual
structure is intermediate between the two Lewis
structures and is said to be resonance hybrid.
The phenomenon is represented by drawing The resonance structures are arbitrary and
-- _
all the probable Lewis structure andputting doubl; imaginary and have no physical reality since neither
headed arrows between them*. The actuil struc-
of the two ozore structures, can be prepared in the
tures is intermediate between these. Thus O,
laboratory.
molecule is represented as
.Thc designation must be carefully distinguished from lhe dcsignation
teaction The double hcaded arrow does not have aDy ijFamic significance iit mercly implies that the molecule or ior
-
represcrtcd by both shrctures than byone of them alonc.
is better
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CHEMICAL BONDING AND MOLECULAR STHUCTURE
6149
Since there are matry molecures rike o, whose behaviour
cannot be explained by a single Lewis
structur€' there is a need for this concept. The resonance
conceDt finds extensive use in expla'ining the
behaviour of unsaturated organic compounds,
structuns : tt is of interest here ro note that the different
",r"fi:"".U$:1ilrt
fiIHl:r resonaring
o-same poitions of atoms (ii\ sone number of shared an d unshared electrons (iii) almost
equal energt.
They differ only in the arrangement of electrons in different
resonating forms.
Examples of resonanc€ structures ofsome more molecules
and ions are given below:
(i) Carbon Dioxide (COr)*
III
That the actual structure ofco, is a resonancc hybrid ofthe above tfuee structures is again supported
both the bond leogths is same (i.e. 115 pm) which
C = O triple bond (f10 pm).
R
EE
AR
il I
z
S
C C
I
C
N
-r"\-
:o: \
IA
:o: :o:
I :o:
I
IIT
o .-- s.--a
III
Dewar structures
ion.
(iil) The resonance hybrid has lowcr encrgv
ond hen.e grcuter slability than uny of the
con-
CONTRIBUTING
STRUCTURES tributing structures
(CANONICAL FORMS)
III (iv) Greater is the resonancc energy, greater
is the stabiliw of the molecule.
II
(v) Greater is the number of canonical forms
(, I
with nearly same energy' greater is the
(!
UJ
"rp".iuttyR
stability of the molecule.
EE
zL! RESONANCE
ENERGY Clarilication about certain misconceptions
AR
in Resonance
real existence
C
S
presented bY a
IA
IIT
Bondorder = gstructu.e"
o- o o-
ofcarbooaie ion,
I il
C_ t
e.g. (i) ln case /C\
\' ,/\ o- \
"/
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CHEMICAL BONDING AND MOLECULAR
STRUCTURE
6151
O ._ [3 ,
(/i) In case of benzene, uo'oo'661 =1i2=rs
The observed varue is, however, not exacfly
equar to r .5 due to some other conrributing
structures
R
(ii)
EE
Tlrc size olthe dectonegotiv( utont
.
be ynall. The smaller the size, the grcater
Jlt()4ld
is thu
AR
erectrostaUc attraction.
C
Chlorine
IIT
"
+o ! lllDm
+b
'\ru/"
)Q ee Pm
H+o
C
Alc acids
N
(iv)
highly hvdrogcn bondins causes the association of many
IA
(RCO()H)
--oni il;;""i* hut in"carhorylic acids, the hydrogen
IIT
1l
11 R
ALCOHOLS
-d +d -d
- arc knolrrl
crlstal asva^d"t.*-11lll1*I""iJli;t";ffi>;ila.; on.l > r?n.rerwaal's forces
Eleatrostatlc lorce
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CHEMICAL BONDING AND MOLECULAR STRUCTURE
6153
,rn *n"" b"tween Hydrogen bond and Covalent bond. The
maia points of difference are given
b"lorj:
COVALENT BOND
(i) lt i[volve6 dipole-dipole attraitive interactions.- (4 It invohrs shariog of
(i4 It is formed b€tween a hydrogen arom and a highty "l"ct.o^.
(rr) It. is. formed between
electronegative atorn such as E O and N. -
two electronegativc atoms
wiich may be of the same elcmeor oi of differeDt
elemeDts.
(rii) The strcngth of this boDd is very smatt. e.g. boDd (iii) The bond strengh of this bond is sutficieotly high
streDgth cf H..........F bond is 41.8 kJ mof-r. e-&, bond strength of H-H bond is 433 kI mol-r.
6.. Elfects or Consequences ofhydrogen
bond-
ing.: Hydrogen
Hydrogen bond helps in explaioins tie abnor_
explaioing the alnoi_
mal physical
physrcal properLies in serveral cases. Some oI
nf
the properties affected by H-bond are given
below:
R
EE
AR
C
S
N
t50
IA
lo I
IIT
a o-
: -50 F
F z
z o-
p -roo o-
o
Z -tso
z
tr
o
6l
LIJ
|
-200
rro
o
FIGURE 6.49, The abnormally hjgh m.p. and
b.p. of H2q NH3 End HF.*
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lrratleelt's Ne.4 Courie Chem ist,,rtrfrlD
6154
The enthalPics
same trend as
4e(")
q
HrS, HrSe and HrTe 5
(c) NH. has ligher boilirtg point thsn PH3 ' z
bonding in
I
This is again tecause there is hydrogen t2
NH3 hut d,
s R
EE
t
AR
i
van dcr Waals forces also increase
C
S
N
IA
IIT
BR
-l
+d
,,lo-...ri H
'--a6./
'o'
I
I.E H*6
t
\
o OH
N
on water. i
t^\ar'
IIT
rhydrogen bonding.
bondiog prevents ai_
a contraction of sizc
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ijrrr C :' r l;'s N eul'Go utie, Chem.i qt'S,,WID
6/56
R
EE
AR
Q'l.Writethel.ewisdotsymbolsandpredictthevalenciesyouexpectforthefollowingelements:
Nitrogen, Fluorine and Neon
C
:r:(valency =7or8-7 = 1) i
S
3iie3(valency=0;
.tns. :N.(valency =5or8-5 =3) ;
N
IA
IIT
'J ": OutofNaCl and trIgo, which has higher lattice cnersr and why ?
turs, MgO has higher lattlce ener6y because each ion carries two unit charge whereas in NaCl each ioa carries ooe
unit charge.
,1 ,
Why secood electron nmnity ofan elementis negative or second electron gai[ enthalpy is positive ?
Ans. AIter the additioD ofthe firsr electron, we gef a ne[,ative ioD which has, therefore, a Degative tendency to gain
anothcr electron ie. encrs/ is requircd for adding the second electroD.
. Why NaCl is o hxd (oDductor ofelectricity in the solid state ?
tus' In the solid state, Na+ and Cl- ions are riot free.
t ) s Why N6CI gives a rvhite precipitate with AgNO3 solution but CCla does not ?
Ans. NaCl is an ionio compound and henc€ gives Cl- ioDs iD the solutioD whicb combine with Ag+ ions giveo by
AgNOj to fornr a white precipitate ofAgCl but CCll is a covalent compound and does not give Cl- ions.
..,'r \yhy reaction l)etween NaCl a nd AgNO3 is very fast but reactior between H2 snd Clr is slow ?
Ans. NaCl and A8NO3 are ionic conlporrnds. In solutron, NaCl gives Na+ and Cl- ions and A8NO, gives Ag+
ilnd NOt ions. The oppositely charged Ag+ and Cl- ions combine immcdiately. The reaction between H2
ard Clz involves brcakiog otcovalent bonds which requires eners/.
! Q I o. Deline lstt How is it related to the stability o[ an ionic compound.
ce enthelpy. (N.C.E.R.T.)
Ans. Definjrion see page 6/5. Greater the lattice enthalpy ofan ionic compound, greaicr is the stability.
, ) , Drrw the Ler?is struct[res of the following molccules and ions and ions and tell in which case/cases the
octet rule is violated
CO2, SO2, BeCl2, NH3, AICI3, PCls, CO3-
R
EE
., t- .^' -12-
C
:'cr
H L J
N
:cr: :bi:bl:
IA
IIT
(r -t trvhy two hydrogen atoms combine to form H2 but hYo helium atoms do notcombine to form He, ?
Ans, Refer to the text (oD the bass of (i) New forces of attraction aod rePulsion and (ii) orbital ooDcept).
(' , , why free rototion obout r r-bond is not possible?
Ans. The ovcrlapping vanishes arld the boDd break.
i) ll Ortofdand ir-bonds, rvhich one is stroDger ard why ?
Ans. o-bond is srronger. This is bccause o-boDd is formed by head-on overlappiDg ofaion:ic orbitals and therefore
the overlapping is large. JI-bord is formed by sideway overlapping which is small.
Q. I 5. C-II bond lengths do you expect in C2H5 , C2IIa atrd C2H2 nnd why ?
What order of
Ans. C-H (C2H6) > C-H (c2H4) > C-H (c2H2). This is b€cause hybrid orbitals of carbon invotved in
overlapping wlth 1,r orbital of hy<lrogen are sp3, ,rpz and sp respectively and their sizcs are in the order
tp3rspz>sp.
,.) ri Arralge the following in order ofdecreosirg bolld sngles
(, cH{, NH3' H2O' BF3' C2H2 (ii) NH3' NH2-' NH{+
ans. (i) C2H2(180) > CH4 (109" 23') > BF3 (120') > NH3 (107") > H2O (104 5')
(it) NH4+ > NH3 > NHt
'llis is because atloftheor iDvolvelf hybndizatiol. The oumber of IoDe pair ofelectrons present on N-atom
are 0, 1and 2 respectively. Grealer the number of lone pairs, greater are the repulsions on the bond pairs aDd
heoce snaller lS the aDgle.
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6/58 Pratlce y s Ne.l Coutse Chemistrglfiffi
() t r' Which of the follordng molecule/molecules will have zeto diPole mometrt ?
CO2, H2O' CCl4, cHCl3, BF3, BeF2, NH3.
H
J-Cr bond) H-Lcl
C
J,
N
HHH
IA
ttl
IIT
(N.C.E.R.T\
Ans, Bond order-Definition s€e page 623.
Molecule: N=N O=O C=O
Bondorder: 3 2 3
Q 2i. Expfoin why dipole moment ofhydrogeD halides decreases ftom HF to Hl. (N.C.E.R.T)
Ans. This is because electronegativity ofhalogen atom dcreases from F to I- Henc€ the polar character decreases
aDd so is the dipole moment.
Q 16. Represe[t diagramaticslly the boDd moments atrd the rcsultlnt dipole moments ln
(i) SO2 (4) cis and tratts fomts ot C2H2CI2
*"t"-rli\-, +21 ts
(n) H-=c-o
+*
01,)H-c-cr
ll HResultant
(N.C.E.R.t)
cJ-n H-C_CI
Resultant F
aran -(/t = 0) cis-01 + 0)
Rcdultallt =0
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CHEMICAL BONDING AND MOLECULAR STBUCTURE
6/s9
(l ll. Predictwhich out ofthe following molecules will htrve hlgher dipole moment oEd why
?
CS2 and OCS
(Nc.E R.r.)
++..i-+-
Ans' s = c = s and o - C = s both are liDear molecules but bond momeDts iD cs2 caDcel out so that net dipole
momenr=0.ButirOCS,bond-.^T:nl9{C=Oisnorequat lo that of C S. Hence ir
= has a net dipote
moment- Thus dipole moment of OCS is higher.
Q 23 From eoch ofthe follolding pslrg select ahe Drolecul€ eith highcr value ofthe property mentiotred against
eoch pair :
(i) NIIJ. PI13 : bcnd angte (r, Nli, NH3 | dipole momeDt
(iii) IUpo. CllO: hxrdness (iv) HCl, HBr : ionic character
tus. (, NI{3 (,i) NH3 (,,r) MgO (,v) HCt
Q. 19 Write the stt[cture of an anion which is isostructural with BF3 ond the structure of a cAtion which is
isostructural with CH4
Ans. (i) NOr- (liiangular planar) (,i) NH{+ (tetrahedral)
(l {!. Dftrw
.r the shnpes of the following hybrid orbitals : sp, spz and sp3 (N.C.E.R.T)
Ans'
l,oo
R
EE
AR
109a 2g',
C
S
N
IA
IIT
All the hybrid orbitals have same shape. However their sizes are in the order sp < spz < tf
O€Ca(}>-
sp sp2 sp3
(.) I I Expl[in how the valence bond theory accounts for
(i) a carbon-carbon double bond (C C) (j) a carbon_carbor
= triple botrd (C = C) (NC.E.R.T.)
Ans, Explain with examples ofethylene and acetyteDe (page 6/39 and
6/10).
Q -rl. Exploil why CHl has tetrahedml geoDetry and rotsquar€ planorwith car.bon
atom at the centre anal four
H atoms at the corners ofthe 6quare.
Ans' Thc hybridisation of csDtral c-alom
is s1 and not rlrp2 (as no rJ-orbital is available for perticipalion). Hence
square planar geometry is Dot possible.
i.r,'NnmethetypeofhybridisationofeachC.atomiramoleculeof(j)propylene(propene)(ii)propyne
Ilow mrtny a and r-bonds are preseDt iD each cflse?
t2J
Aus. (i) CFI3-CH = CH2 (C-1 is rp3, C-2 and C_3 arc rp2), ,_bonds = 8, z-bonds = 1.
123
(n) CHr-C = CH (C-1 is rp3, C-2 aDd C-3 are
ry), o-bonds = 6, -bonds = 2.
r_,,: Which hybrid orbitals are used by carbon atoEs
in the followitrg molecules ?
(i) cH3_cHo (i, CH!_COOH.
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Nc.4 Course Chent i stYtl
6/60
H..
\l 2./,H
Ans. (i)H-(l-c\. c-l is,rr3 hybridised
-
l7' o c-2 is,rf hybridised
H-o 2.//
\l
(ii) H C-l isrrr hyhridii'cd
H -C-41
'/ \o-n
,r rr ln SFa molccule, the lonc plirofelectrols occupies irn equttorial Positiol rother thltn oxilrl J'ositioo ill the
lvlly ? (N'C E'R T)
oversll trigonal bipyramidal arrsngenrent'
Ans.Thc/p_6PrePulsionsarolessifitoocuPiesequiltorialpositiol]thanifitoccuPiosaxialPositio[..4'saresult,
is l"ss and stability is more (sec pagc 6/44)'
"nerry
U r' Explain how VIt theory differs from Lewis concepl
hy muluul \h;rrin! oI clecltotls whereus accordil1g
Ans. (i) According lo Lewls concepl' il coYalcnl holld is l()rilleJ conlirlllilrg eleclrons u ilh
to VB theorY a covalenr hond ls lo;nlcll by thc t1\'crh11 ul hrrit'-llllc''l at'rntrc
'irhilills
opPosite sPin.
shaPes ofDrolecules whcreas Le$is concept cannot'
0i) VB theory can explain the
(iii) VB theory can exPlain tbe strength of bonds wheroas Lewis concePt cannot'
Q. -17. D€scribe the change in hybridisotion,
ifany
(4) oiAt otom ltr the r€action AICL + Cl- -. Alclr ?
-.- R
F3B-NI!3?
EE
(r) olB ard N stoms in the reaction BF3+NH3 (N.C.E.R.T,)
AR
lr,.onthebasisofVSIIPRtheorypredictthesh,lPcsofthefollowingmolecules/ions?
c2u2 II3O+ (v,P2O (zii) PCl3 (riii)
IIT
Ans.(i)TLtrahedral(i)v.shape(iii)Tetrahedral(iy)qllndrical(f).liigooalPyranridal(vi)v-shape(yii)Tiigonal
pyran]idal (riii) Tiigonal bipyranlrdal'
i,) l'r Why axial bonds ofPcls are lorger thnD cquatorinlbonds ?
pairs by the equatorldl bond pairs of electrolls-
Ahs. This is due to greater repulsion on the axial bood
, wlry NF3 is pyramidal h t BF3 is triangular plrnrrr?
hy lone pair of electroos bu t in BF3' B has the
Ars. In NF3, N has the hybridisatio[ d with one positiorr occuPled
hYbridisation.tf
'lriWhybordaugleinll2oisnearlyl045'hutthatinII2S'itisrcarly90'?
Ans. Refer to the text (PaEe 6144)-
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CHEIUICAL BONOING AND MOLECULAR STRUCTURE
6161
i Draw thc str cture ofll2SO4. wlrat is hytrridisation ofS.atom in it ?
o
I
Ans. Il-O-S-O-ll Hybridisarion of S-arru is ri-u3
J
o
Out ofp-orbitfll and sp.h)brid orhital ryhich has greflter directional charflcter and l"hy ?
ars' .tP-orbital has grcitcr dircctlolral character lhan
I,-orbital. 'lhis is bccause p-orbital has equal sized lobes with
equal electron dcnsitY in bo(h lhc lobes whcres .tp-hybrid orbiral has greaGr electron den:siry
on one side-
Expltin the important aspects ofresonahce r"ith reference to CO3- ion.
W,C.E.R.T,)
Ans. see resooating srructurcs on pagc 6/,19. ,,\[ the lhree bonds arc exactry idenrical in bond
st.cngth and bond
length.
. II3Po3 cnn be rePresented l)v thc strtlctn res I r nd ll shown belorv. Cnn these two structures
be taken os the
cnnonical forms ofthe reson:rnce hybrid ot I13pO3. If not. state reason for the sam.
H
II:O:P:O:II II:O:P:O:H
:o: :o:
llt
II
R
EE
lN.cE"R-T)
A[s. No, these cannot be taken as c€oonical forms becausc the pcitions ofator's have be€n clranged.
AR
AnB. In ll2o, there is hydrogen bonding and heDce association of H2o moleqrlcs but in H2S there is no H-bonding.
S
(.,. .lb
N
Ans. In HF ttlere H-bonding and he[ce the molecules are assoc.iated together but in HCI therc is [o H-bonding.
is
IIT
Ans" bolllng pornt l,cre{ses. \thy ? or out of Hrl HCr , HBi nnd til whtch has lowJt bo[r"8
[.JH:},,X#;itrH"*-H*,],r.'il1fl;'"HH':l{
e.r"t ;;;1; t--
-l
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NeqJ Coarse L lretu is lrq
6162
Ans. Each H2O molecule forms four H'bonds, two with o'atom and
two with H-atoms Further' each I'I2C)
molecule is linked to four HzO molecules through H-bonds tetrahedrally'
why ?
V 5 ('. Out of..,-nitrophenol ard p-nitroPhenol which hns higher boiling Point nnd
point because there is internolecular H-bondingwhile iD o-nitrophenol thcrc
.a.ns, p-nitrophenol has htgher boilinE
is rul ranlolecular I{-boDdinI
(J. 57 Though Cl h{s nerrly same electronegativity as N' yet there is no H-bonding in IICI'
r hy ?
Ans. Chlorine atom has a large size-
(J. 5E. why ghrcose, trnctose' sucrose etc' are soluble in water though they are covalent comporlnds ?
with water'
Ans. These conlpounds contain frolar -OH groups which can forfll fI-boods
l) 59. Jlenzene ring contEins alr4nste singlc and double l'ondq yet all the C-C honds are ofeq[allength' Why ?
Ans. Ir-E
C
Q 6l. Why is water a liqnid whereos H2Se is a gas ? (I.S.M. Dhanbad l99il
S
N
Q. 65- t#hy an ionic bond is formed between tvo elements having large dilference in thGir electronegatiYi8 ?
IIT
(Bihdr 1997)
electrorrs to such a |arge exteDt thaD the othcr
Ans. 'fhe n,]ore electroDegative element will atrract the shared Pair of
that it will amouDt t6 transfer ofelcctron resulting in the formation of ioDs'
bond angle ?
Q. (16. Which ofthe following has maximum
H2O' CO2' NIr3' Ctl.. (Bihar 1997)
Q. 12. Predict the dipole morn.trt of a molecule of the type AXa *ith square plflnar armrgemcnt ofX atoms.
C
Ans. zero.
S
Q. 13. Identlfy the compound/compounds i[ the follorving in which S does not ohev the octet rule.
N
so2'sF2'sF1,sF6
IA
IIT
,"t tt six
"i"""
A to the atom B.
C
13.
it help to predict the stability of
Define Lattice enerry. On what factors does it clePeDd How
? cloes
14.
the ionic comPound formed ?
15. How caD the electron affidty ofchlorine be determined usiog Born'Haber rycle
? (rVC'Eft'I)
what are the condilions
Scc.6.9 ii, *t lr r*n, ty a covaleni boncl ? Explain with three suitable examples
nr 6.l5 for ",
the formation ofthis tyPc ofbood ?
qHz'
17. what are l,ewis structures ? Write the Lewis structures of Hz , F2, H2O, NH3 ' qH4 and
src,, !;. 26. DeliDe the term Electronegativity. Explain itwith onesu(able example.I{ow does it helpin predicting
, (, l o
r whether a covalent bond ts polar or non-polar ? Explai[ each case with oDe example.
27. Define'ElcctroneEativity'. I{owisir calculated on (i) Pauling scale (ii) Mulliken scate
IIow are the two values rclatcd to each othcr ?
2E. Which of the following hydrogen halides has the most polar molecules and why 'l
HI, HBr, I{Cl, HE
29. HIr is nrcre polar than IIt. Explain why ?
30, What do you understand by partial ioDic character of covalent bonds?
.11. Define Dipole moment. Draw dipole diagrams of H2O aDd BF3.
32. Explaro : Each cirbon{)ry8en bond in COz nrolecule is polar but the molecule ilself is non-polar.
33. Explain thc ternr Dipole momenl. Name two molecules which have a dipole moment and two
molecules which do not have a dtpole ntontent. What is the sigDificance ofdipole moment ?
34, Explain giving rcasons. which of the follo\ ing molecules have elecrric dipoles
(d) CCta (b) CHCtr (c) CH2C|2 (d) CH3CI (e) CHn.
35. Give reason for tbc following:
(i) lonic conrpounds are soluble in waterNhercas covalent compounds are mostly insolublc in water.
(ii) Ionic compounds have higher rnelting points than the co\"lenr compouDds.
(iii) NaCl solution gives a white ppt with A8NOJ solution but CCl4 or chloroform does not.
s( ( /, l-r J6, What arc the nrain postulaics of Valcncc Shcll Illcctron Pair Rcpulsion (VSEPR) thcory ? What
r,, 6 .lI improvement was Dradc bv Nyholm aod Gillespie ?
37. R
What ts hybridisation ot orbitals 'l Dra!,, ourline sketches to show the formation of .rp ,y2 and sp3
EE
hybrid orbitals.
AR
3tl. What type of hybridisation is arisociated with thc central atom when the atoms attached to it lbrm
(d) an equrlatsral triangle (r) a regular tetrahedron ?
C
39, E\plain wh),carbol has a lalenry offour and not two and why are the four C.H bonds in methane
S
N
idenlical.
IA
41. Carbon has electronic configuratron I s2 Ztz 2p2 a\d.lhercforc, should be bivalent. Howwillyou justiry
its tgtravalency irl methane ?
4. How can thc lattice enrhalpy of aD ionic compound like NaCI be determlend try using Born-Flaber
(rycle'l
C
Ste.6.9. 5. Explaio the forma(iol ofcovalent boDdon the basis of (i) l-ewis coocept (ii) Valenca Bond lheory,
S
6. Briefly describe Valence Bond Tbeory of covaleot boDd. How cao you iDterpret it in terms o[ enerry
considerations 'l
IIT
7. Whar arc sigma and pi bonds ? Explain the different wals of their formatioD diagrammatically. Which
one of them is stronger aDd why I
scc. 616. t. Explaio the terms bond length, bond energy and bond angle.
9. Briefly explain quantunr theory of covalent bond formation.
sr!.(,.i1 10. What do you u nderstand by partial ionic character of covalent bond ? How is it calculated I Explain
r,,r,.:o. rakingexampleol HCl,giventhatitsobserveddipolemonrentisI03Dandbondlengthis1275 A
t l. Define dipole moment. Discuss its important applications.
12. Why are some covalent bonds polar ? What is a dipole ? Ho\r, can a Drolecule that has polar bonds be
a non-polar molecule ? How do dipole moments of molecules of CO2, CHa, H2O and NH3 help iD
ascertaining their structure ?
Src.6.2l. 13. Listvanous characteristics ofcovalent conrpounds. DiffereDtiate between electrovalent aDd covalent
1,,6.:1. coD)pounds.
scc.n.2.1. 14. What is meant by hybridisation of atomic orbitals ? How do€s lt explaiD the sbapes of molecules l
t,r 6.25. lllustrale your aDswer with suitable examples.
15. What is VSEPR theory 7 How does rt explain the bond angles observed in CHa, NH, and HrO
molecules?
srr (',-2(, 16. What js a co-ordinato bond ? Explain the formation of a co-ordioate bond. Describe it in orbital
overlap concept taking an exanrple.
sf,- 6.:7. 17. What is Rcsonance ? Explaio with a suitable example. Deline ResoDaDce enerry.
str'6.lli. lE. Whatisa hydrogen bond ? What requiremenl,s should a molecule fulfil for theformation ofhydrogeo
bond ) Explain the formatioo of hydrogen bond in HF and NHI molecules. Discuss intramolecular
hydrogen bond.
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F Resuftant
of 3 N-F
bonds
Th us Mereas resultaot moment of N_H boDds
parrly cancers the resulrant momert of rone pa,r.
adds up !o the bond moment of lone pair, that
ner"e tt nlt J[i"-,,oir,"iitr.rr,
of 3 N_F *"*
bonds
"
i. i"[ ol"-,iri ir NH,
.., 'i 2. Comparison of bond
dar io shapo with one rone
pl* o, N ;;;;;;;;;;
ivrr,.". ,t o"roprio
"
oi"r""i racted more towards F in
6/67
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6/68 Neut Course Chemistrq
Note- PH3 and PF3 are atso pyramidal in shapewith one lone Pair on P. But PF3 has Sreater bond ange tban
pH3 (oppcite to NH3 and NF3). This is due to resonance in PF3 leading to Partialdouble bond character as showrr
belor, :
Asa result, repulsions berween P-Fbondsare largeand hence the boDd angle is large.There isno Possrbihty
for the formatioD ofdouble bonds lrl PH3-
R
EE
Elfect ofthe type ofhybridisation on the directioll ofpolority ofs bond and magnitude ofdipole moment.
3.
For example, thedirection and Dtagnirude ofdipole moment of C-H bond in methaDe and ethylene are as follows :
AR
H
C
4. Sugden's concept ol stnglet llnksgc. Sugden put forward the view that octet rule is Dever violated. He
IIT
suggested tiat in case of moleqll; like PClj, SFa etc., some atoms are linked to the c€ntralatom by covalent bonds
wbile others arc linked by singlet bonds.,4 ringkt bond b fomed by one sided sharing of only one electton between
the r,)o o,torns atd is thirefore repesented, by half dnow ( ------t ) pointing from donor to accrptor. Thus we have
It can be s€en that
cl FiF
\ t,/ S'
t\
I
FIF F
cl
No. ofsinglet bonds = Tbtal no. of bonds-No. ofelectrons required to complete the octet'
5. PolarlsiDg power and Pols ssblflty (Faien's Rules). Although irl an ionic comPound, the bond is
just as covalent bond has some ioDic
considered to be 1i6% ionic, actually it has some colralent character. Thus
character, ionic bonds have somc coval€nt chamcter' This was exPlained by Fajan as follows
:
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CHEMiCAL BONDING AND MOLECULAR STRUCTURE 6/69
4D_Drrlo,N4!:.!lqEFU!!ry_EqB!!4ILqN9_o_1id
When a cation appr@chcs an aDron, the eledrco cloud of the adm b attracted to$,ards the cation and hence gets
distorted. The effect is crued pol$isstion of the aDioD. The porver of the catioo to poladse tbe aDioD is called its
polarlshg polder and the leDdency ofthe anioo to 8et pohris€d is called iLs pnlarisabitity The greater is the polarisation
Produc€d, more is the neutralisatioo of the chargcs (ie. charge of the catioo by the clecilon cbud of th€ anion) and
hence the ionic character de.reas€s o. the covaleDt cbaracter incf,eiscs, Tho propertiGlikc melting poinq h€at of
sublimatioq solubility in vater or oon-polar solvents change accordingly. The polarising porver of tha ca6on and ttle
polarisability of the aoion and hence the formation of cotr'alent botrd is hvoured by the following frctoN:
(i) shall size ofthe cltion Smaller the calio4 geaterb its plsititgpolrr. This sxplains why LiCl is more
co\r'alent than KCl.
(il) Irrge slze ol the anioa. l,arget ,he anio4 greoter is itt pobri.sabirry (because the hold on thc electron
cloud by the nucleus decreases). This €xplaiDs why covalent characlcr of lithium halides is in the order
LiI > LiBr > LiCl > LiE
Ttrat is why their melling points are in the order
LiI < LiBr < LiCl < LiF
c) (s47 c) (513. g (&70'c)
(446"
(iii) l-arge charge ou the cation or anioo. Larger the chorye on the catio\ gredter is itt polori:ing power
(because the electron cloud of the anion is more easily and strongly attracted by the catioo). Hence covalent
chamcter iDcreases. That is why the covalent. character of rhe chlorides is in the order
is more cotr'alent
than Na+cl-.
C
6. Applicrtion ofVSEPR ttrdory to cohplex holecules Le. Dot havltrg only otrc crltrsl atorr- Let us explain
S
HO
IA
IIT
"_t_J_;,
I
H
The first C-atom on the left has 4 bond pairs only, therefore its gcometry is tetrahedml. Ttre second
C-atom (centralC-atom) has 3 bond pairs (countiDg double boDd as one bond pair). So itsgeometry is trigooal
planar. Tbe Dext atom viz o- atom has 2 bond pairs and 2loDe pairs. so ir has a beot geomltry. combining alt
tbese Eeometries, we get the overallgeometry ofac.etic acid as follo*s :
The above structure can also be written on the basis of hybridisatioo. Hybridisation involved will be :
C-atom, sf,2oa C-atom, ,l, Dext O€tom, ,1 (with rwo orbitats containilg tone pairs of electrons).
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6no N e u, courle Che m is t r7\fififi)
bond i.s diircctional. In ionic compounG, each ion is van der Mal's forcqs anroDg their nrclecules-
S
su rrou nded by a Dumbor ofoppcitely charged ions (ii) Therc is hydrogen bondrng in II2O but no
N
(ri) CCla atrd Sicla ore tetrah€dral Ans. Applying FaJan's rules, tho result cin be obtaiDed
in each case, as follows :
(n'i) The HSE bord atrgle in H2S is closer to 90" (i) AtI is more covalcnt than AgCl. Thls is be-
thon HOH bond angle in II2O cause I-
ioD is larger in size than Cl- ion and
(i) Ir BF3, B-atom undergocs rp2 hybridisation. hence is more polarized thrn Cl- iLrn.
(ii) Beclz is more covalent rhan Mgclz. This is
Hence BFj is triaDgular planar. In NH3, N-atom
bccause Be2r ion is smallcr in,size than Mgz+ ion
undergoes ,rp3 hybridisation- Hence NH3 has
and hence has greater polarizing powcr.
pyramidal shap€ with one lonc pair oD N-atom.
(iii) Sncla is more co!-atenr rhaD SnCl2. lhis is
(.i) Both C in CCta and Si in SiCIa undcrgo.rp3
because Sn4+ ion has greater chargc aitd smaller
hybridisatioD. HencE they are tetrahcdral_
size than Sn2+ ion and hence has greater polariz-
(iii) Refer to pa8e 6/,14. rns power.
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t:, r'.t, .t,'-- Neur Course Chemistql&M)
6172
(iv) CuS is more colalent thaD CuO. This is i.) 'i) Account for the folloving: (Writc the ns\ver in
forrr sentences onlY.)
becauscs2- ion haslargcr size than 02- ion anJ
'fhe experimcntally determined N-l' hond
hence is more polarized than 02- iol'I.
length irr NF3 is gre:rter than the sum of the
Givitrg reasons in brief indicate whether the
sinple covalcnt rrtdii ot N .ind l: O.I.T 1995)
followilg statemenLs is TRUE or FALSE,
Ans,'Ihis is because bolh N aDd !- arc sn'lall aDd heDce
The presence of polar honds in o polyatomic
hxve high elcctrofl density. So lhey repel lhe
molccule suggests that the molecule hns holr-
(I.r.T tee0) bo[d pairs thereby n]akiDg the N--F boDd length
zero dipole moment.
larger.
Ans. False because in synmetrical polyatomic
orolecules like BF3, CII4, CCl4 clc, bonci mo- .j r (;ive renson for thc folloving :
The molecule of MgCl2 is linenr while tllat of
nle[ts cancel out aDd thc net dipole mor]cnt is
zeto. staIlhous chloride is aIlgular'
(M.L.N.R. Allahabad I 995)
Write trvo resonating structllres of N2O that
s tisfy the octet rule. Ant' E c. of l2Mg is Ltz 2tz 2p6 \'i2 in thc gr(lLlnd
(l.I.T 1990, M.L.N R. Alldrubad l99j) srate. lleDce in thc excitcd stale. iL is
ltz Ztz 2p6 3|t 3d. It ur:clergoes rP-hybriclisa-
Ans. 'tj = il = o : ** :N =N - ci :- tion.'lherafore lhe shaPe of Mgclzrs lincar ll.C.
of SD is IIkl 5r25p]5pj. It undcrgoes 72'
Q&ange tbe follorviDg in order of itrcressitrg hybridisation. l'he two hall-Iilled hybrid orbitals
strcngth of hyitrogen bonding (X......'.H-X). form bonds with Cl-atons whilc lhe third is oc-
o,4s,cl,N cupied try a loDe pair. Hcnce SnCl2 is bcnt or
(I.I.T. 1991, M.L.N-R. Allahabad 1993) R
V-shaped.
EE
ADs. Cl<S<N<O<E rJ l1 Explnin why the diPole moment ofNfI3 is more
AR
(l 6 Write two resonance structures ofozone which than thnt ofNF3? (ltoorkee 1995)
satisfy th€ octet rule' (I.I.T 1991)
C
ii
,rt9x
i (v- shaPed or angular)
u -/,2' \.
FFFF y/
Thus the central atonr (O-atom) has 4 pairs of
electroDs (2 boird Pairs and 2lofle pairs) Herlce PC13
oxygen in OFz is.lf hybridiscd aDd the moleculc No. of electron pairs around P
is V-shaped. 5+3 8
Oxidalion state of F=- l, OxldatioD statc of O
=--z--1=4
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CHEMICAL BONDING AND I\4OLECULAR STRUCTURE
6173
dehydc is o high EcltitrE 6olid. (I-I.T 1999) In BrF5, number of electroDs in the valence shell
C
is no further association amoDg the molecules r',€. boDd pairs and otle lone pair. Hence, hybridiza_
IA
they exist as siDgle molecules. In case ofp_hydro(y tion is rf I and the shaP is square
Womidat
IIT
ct
I (, l') What is the S.I. unitofdipole homent ? Draw the
H LEwis dot diagEms of nitric acid. srlphuric acid,
o-hydrox] benzatdehyde phosphorous acid and hy,pophc;phomus acid,
IItrantolecular-bondiDg (West Bengot Jj.E. 2003)
No association Ars. TheS.L unitofdipole moment is C-oulombmetre
o ..{O}o-rr...o = c-@o-rr ... (Cm), 1 Debyc = 3 335 x t0-30 Cm. Lewis dot
\.:J
| \::-/ | structures ofthe given acrds are as follor{s
HH :
p-hydrory beDzaldehyde
r],
Intermolecutar H-bonding
H-O-N- O:
.. ' I
Association througb H_bonding
H-O-O-O_H
As a result. o-hydroxy beDzaldehyde rs a liquid
ll
O :O:
J-
while p-hydrory b€nzatdehyde is a high nreliing Nilric acid
solid. Sutphnric acid
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Pradeep's
6174
:o: tI ,,=,q;7;z^*,*"
..t
H-O-P-O-H a-l-o-r,
"T urro ={to,,}o^*,,}o "^ *
-t ,
F Solution.
l_-___--:--
TiigoDalliprramidal Squareplanar p,ro = ! pLn + af," + 2P$, cos lo5"
(rldhybridisation) (,ty'd2hybridisation)
(J 21 State with rcasons :. (1.84)2 -2pLH+zPbHx Q 2588)
(i) Which is Eore acidic-anhydrous HCI or
oqueous HCI ?
3
R 38s6 = zpbHo -0 2588)
EE
(ii) Which is rDore polar or N2O ? - 751 = - 75'l
-CO2 [cos 105" = c.s (180 cos
AR
Alrs. (i) Aqueous HCI is more acidic For reasoD see or pzo' = 2 2839
S
N
Ans. to Q. 1,Pa86171.
or loH=151 D:151 x10-18esucm'
IA
H-O-H botrd angle in HrO molecule, giver that the 2 6 x 10-10 m. Calculate the .liPole moment of KCI
molecule. if there were oPPosite charges of one fun'
bond momentof 0-H bond is 1 5 D'
dameltal ullit locoted Et each nucleus. Cnlculate the
. As diPole mo- percenisge ionic charocter ofKCl. (r.r.T 1993)
ment of H2O isthe resultalrtof
(o-H boDds), there wcre oPposite charges of one
If
thetwovectors
therefore, if a is the anSle be- fundamental unitic.4 =7'fi2x 10-le coulombs, then
tween the two vectors, then p_qxd
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CHFfuIICAL- BONDING AND MOLECULAR STBUCTURE
6n5
= (i sC2 x 10-19 coulombs; x 12.6 x l}-to m) = 64.2 kcat mol-l = 26E o kJ mol-l
-- 4 1652 x- lo-29 coulomb metre ,. lxu-xrl = o. t1z,/6i8.6 = 1.67
Fobscocd = 3 33r x t0 -29 columb metre Astp > XH, xF=7.61 +X,H
.. io[ic chafidet
7o = 1.67 + 2.1= 3 17 =3 E
3 336 I lo-11 x /?o6,lz11 5. fuihydrous AlCl3 is covalenL From the
l0o=E0.09%
i 1652 x l0-zY data given below, predictwhethcr itwould rcmain cora ent
or becolne ionic in aqueous sohltion (lonization eneq5/ for
AlCl, = 5137 ld mol-1, Alllya,"ti,n for Al3+ = -4665
lu-g = 1t)4 2 kcal rnol-1, kl nrol -1, AIInr^.! for Cl- = -3t1 klmol-I.
[. r=-r,i 6kr:al lnoi-I, (I.I.T t99n
Solution, AlCi3 {rt - aq A](l: r,r{t
li*.-, = 134 6 kcal mol-r ,M.L.N.R. tgg6)
- -
Sotution. Suppose thc electroncgativlties of[I aod
r'J3+ roql .lC| Oqt
'lbral energy releascd on hydrarioD of I mole of
F irr. .eDr.seoted rs IH and tF. Applying pauling's
iorD'lul,.r
Al3+ ions and 3 moles of Cl- ions
LE CHOTCE atrsnoNs
C
S
For CEs
N
IA
A p,-.lrr covalent bond $ formed by (c) orbitals ofsane atom but with widely different
fr) lraosference ofone electron energies
(, ) iranrt?reoce ofoDe or ntore electrons (d) orbitals of different atorns with diffeient encr_
i./ ih.iring ofone electron ges
(.i) rh?riog ofoDe or nore electroft\. (e) orbitals of the same atom with exactly equal
energies.
Dip,ile rloDteot ofBeFz is
5. Which of the followiDg stateme[ts is wrong ?
(li) very iow (b) very higb (a) Covalent compounds are generally soluble in
(r) zcro (d) Dot definite. polar solvents
3. Cir5.r!'t u ethyiene involves the hybridisarion (b) CovaleDt compounds have low melting and
a) sp3 (b) tpz boiling poiDts
it,t )P (/) Done of these.
(.) Ionrc solids do nor conduct elecrricily
4. lL hiidisarion involves (d)Ionic conlpounds coDduct electricity in the
l// I ..rr-rrrals of same atoo] with sligh y different fused state.
{jIergtes \tr1o2 is isostructural with (one or more)
f/) I rrrl\itals ofdifferent atoms bu t wlth equal energies
Wne"\ (6) SnCIz
( M. L. N.
n.)ent is :
S
(a) NH3 (6) CHC|3 19. NH3 and BF3 fotm an adduct readily because they
N
IA
gWct+ form
(c) Hro
bond (6) a covalent bond
IIT
(a) an ionic
(!I.L-N.R. Allahahad I99I I
G)a mordioate bond (d) a hydrogen bond.
What is the maximuD number of hydroScn bonds (M. L.ll'R' Alhlubad l 994)
iD which a water molecule can Participate ?
(o) I (b)2 20. NH3 has a much higher boiling Point than PH3
(c) 3 4l+. because
iM.I^N.R. A ahahdd 1991,1.1.7. i992, (o) NH3 has larger molecular wsight
v.P. c.li P: Ieeg\
(6) N H3 under8oes umhrella inversi()n
'13. The linear structure is assuoled by (one or more)
forms hYdrogen bond
(a) SnCl2 Jgy'NH3
./p')Nco- (d) NH3 contaiDs ionic tronds whereas PH3 col]-
(c) NOr+ t4r6r. G.I.r. IeeI) tains covalent boIrds.
(M.L.N.R. Alldlwbad' I 994i
14. The molecules tbat will have dipole moment (one
or nlore)
21. Which of the followiDg has oet diPole moolent ?
(d) 2, 2-DimethYl ProPane
(a) CCln (b) BF3
p)kaos-2-Pentene
(9INH. (d) coz.
J?lcis-3 -Hexene
(d)2,2,3,3-tefiamethyl butane. (l l1: 1992) (Haryam C.E.E.T 1994)
i:i ili, iii:, i: :i;: ir, i:i:i :: ,:i:i i :i::i:,i:ii:iii:l:ii:iijitl
g+Etharct (b) Diethyl ether 30. Wictr one of the followiug compounds has
(c) Ethyl chloride (d) 'Dicthyl amine. d
hybridrsatioD ?
61.L.N.R 1995) (a) coz
23. The Dumber and typ€ ofbonds betweeD two carbon
,p4'so,
atoms in Caq are (c) Nro (d) co. o.r.T 1es7)
(a) one sigma (o) and ooe pi (') bond 3I' Among Ko2, Alot , BaO2 and NOr+, unpaired
(6) oDe sigma (d) ard tro pi (z) bonds electron is pres€nt in
(c) oDe si8ma (a) and oDe and a half pi (rr) bond (a) NOr+ and BaO, (6) KO, and AIO'
, l!l) one sigma (o) bond (d) BaO2 onty.
'-ffini* of rhe following hydrogen halidc is mcr ;lclAorotrtY
volatile ? (1.1.L 199n
(a) HF Jh)1ict 32. The cylindrical sbape of aD alkyDe is due to
(c) HBr (4 ril. (c) three sigma C--C bonds
(HoD a,ra C. E. D.7: 1996 (6) three , C-C bonds
)
25. AmoDg the fo or,/iog speci€s, idendry thc isctruc- (c) two si8ma C-C bonds aod one ,r C-C bood
tural pairs NF3 , NO! , BF3 , H3+O , HN3
(4) One sigma C-C bond and two z C-{
bonds.
(C,B.S.E. PM.T I9g7,I
(a) [NF3 , NO3-] and [BF3 , H3+O]
33. Which one of the followiDg has highest dipole mo-
(6) [NF3 , HN3] and ment ?
[Not , BF3]
creasing dipole moment would you expect maxinum distance between the
S
0I), o-
GF
IA
poutrd contains the species (4) The electrons are shared between aloms
(a) K+ , F- .ind H+ (D) K+ , F- aDd HF (r) The bond is non-directional
(c) The srrength of the bond depends upon the
ana lP,Frl- (d) [KHFI + and F2.
;!p\A+ extent of orr'erlaPPing
(I.t.T. 1996) (d) The bond formed nray or may Dot be polar.
2t. Among tbe following compouDds, thc one that is (jl.ll Ptl '[ t998t
polar and has the central atom with sp2 hybridisa- 36, Hydrogen bonding is not presenr in
tioD is
(d) Glycerine (D) \lbter
,gfurco, (b) siFl
1q/Hyorogen sulpbide (d) Hydrogen fluorido.
(c) BF3 (d) Hcro2. i|.P PM.',f t998)
(LI.T 1 997, 2000)C. P-M-T, 37. The geometry and rhe r),p€ of bybrid orbitals
29. Which conrains both polar and non-polar bonds ? present about the c€ntral atom in BF3 is
)
(d) NHaCI (D) HcN (a ) linear, rp _lLfirgonal ptanar , q2
l2.a Z3.b 24.b 25.c ZG.b 2i. c ZE.d 29.c 3O.b 31. c
,2. d 33. d 34. b 35. b 36. c
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6l7A Newt Cotn st 4 {ir t;'t, -. '
(c) tetrahedral, rp3 (d) pyramirlal, ,sp3. 45. The correcl order of hybridisatioil oi i.ii! !.:r,tlri
atom in the iolloqing sPccics
(l.Lf, 1991 ; Ha4am C.t').t') Tl
38. The correct order of increasiDg C-O bond len8th NH3, IPtcl4l2-, PCI< and BCl3 is
-q4fco .co, < cozr- . (l.l.T. 19e9) gf*.r,,t ; (r) NH3, BF3
39. In a double bond connecting two atoms, there is a (c) co3'?-, so3- (d) PCrs, IO5
sharing of
(c.B.s.L. M|. l: )001\
(a) 2 electrons Jbf4 electrons
(c) 1 electron (d) All electrons. 47. In\rhich of thc following, bo[d angleis maximun'] I
(Ll.l! c.L.E. 1999) (o) NH: It'tr,rs[
40. Whicb one of the follqwiDg molecules will form a (c) PCls (d) scr2
linear potymeric structure duc to hydrogeD bood- (c.R.s.D, Pitl.T 2ool)
ing ?
(a) HCI
(c) Hro
ffin 4t. Which one of lhe
molecules is correct o[
fcllowing arlingcnrenls
the basis of their dipole
r)l'
QfNtt. moments ?
t(:. R.S 1,. Pll',L 2000\ R
(a) BF3 > NF3 > NH3 (b)NF3>Bt3>Nl[3
EE
41. Which among the following has the largest dipolc (c) NH, > BF3 > NF3 lrNIJr :- Nl-3 > BI;1
AR
moment ?
frro (e) NH, = NF, > BF. lKL th L L.1.. )001)
,I') NH,
(D)
C
(c) HI (d) so3. 49. Bond dissociation energies irf H , l{CI and Iltlr
S
(A.l.l.M.s. 2000)
(a) HCI > HBr > HF HF > HBi > HCi
IA
(D)
42. Atomic orbitals of carboD in carbon dioldde are
IIT
1)f. Wli"t of the following does Dot coDrain co-or- 63. Wbich of the followiDg pair of molecules will have
dinate boDd ? permanent dipole moment for both members ?
(r) BHr- (b) NHt R(a) NO2 and COz (Ql NOz and 03
EE
(c) Sifi and CO2 (d) SiF. and NO2
9"q- (d) H3o+
AR
(,r.r.8.t,.E.2003\
(F.ajastha n l! M.T. 2 0t)2)
C
position to miDinrize
(4) ,rp3 hybridized carboD
(a) lone pair bond pair repulsion only
(D) bond pair
- bond pair rcPulsion only (rf ;? hybridzed carboD
- pair repulsron ard lone pair-
(c) rp2 hybridizc(l carbon
(c) lone pair
- lone
bond pair repulsion (d) Always samo irrespective of iLs hybrld statc
lone pair lone Pair repulsion only (e) None of above llierah C.l':.li. 200J )
{d) - tL.lj.\.1: I: )ll l:,!i1t)11 The H O O bond an8le is [!2O2 is
- -
@) ln" 28' (6) 10e"28',
(c) 104 5" (d) 106'
(a) HzS < Silla < NH3 < BI-3 (f91' \rrala P\I.T 2c04\
(b) NtI3 < H2S < SiH4 < B[r3 If a molecule MX, has zcro dipole moment, thc
ferl{2s < NH3 < SiIJ4 < BF3 sigma bonding orbiials used by M are
(d) H2S < NH3 < BFj < S|II4 t,t I.L.E.E )0(tJt (o\ ip3 d-hyhrid
R (6) \p-hybrid
EE
71. The state of hybridisatioD of boron and orygen hybrid
(c).r?3d2 k/) ?3- hybrid
AR
(c) AlCl3
(c).ruul3 Drr,
Gl) BHr
(c)II > I > IV > III (d) tV > I > III > II \4)
(Otitsd J-D.8.2001) (Haryana PM.T 2004)
I. 2- Dichloro-2-pcntahe
CH"
l.t ' -C-Ct
Il Q.tA)
()-c-cH2cH3
Irans
1
8.
(c
Y
=0
9. [(Nr]zNt12) .-.- Hl+ CI
I t,.
BcF; inlotves ry-hybridisariorr of Be- IV
t2. Each tI2O motecule can fbrnl lruo Hencc rhc ordcr is t\/ < I < Il < lll.
,r-*nd. ?7. KHF2- K+ + HF .
and_ lwo H-h)nds rhrough
$t:.ir-f 9--","1
l-t-aton]s (Sce Fig. 6
r$.o
2t. II2CO3 a-J
5l pflge 6/5-s). 2II+ r OOj_
lJ. IN=C^:.Ol- rnd S= (= Saretinear.
cllr
r4. cr t,-l'-CH-
"t (,, = 0)
CIII
cIIs_C_lI
(tt + 0)
H_c_cH2cl13
Jl. Flectrons prcsenr: NO2+. 7 + 1,_l=22,
cHlct t._c_t r
-il BaOr-56a16=72,
cI13-cH2_c_II AL t o).
R ?\tot=13+16+1=30
cII3 CH3
EE
and KO2 = 19 + 16 =
il
('11.,-(:-1-11
3-5
-lr'
AR
nteDt has
= 0_
highcst dipole moDtent.
lt
IIT
,rP = 1\z L2 2p6 31 3p:34 3p: 34" Cs+ ron is largesl cation and I-
is largest anioD
35. Colalent
- r (. 2_ .,y' hy.r,rirtrsrtron bonds are dircctioDal.
,J. (h" lll . so rl rnvoh.es one sigoru lnd t\\o
38. Thc slructurcs ofthe given specics arc
I /
i
pi nonds.
24, Most.vol tilc hydroge[ h{]lidc ts thc onc N.hlih has
Ieasl hollrng point vrz llCI c=o, , O=C=O.
2-5' NI-, auo
H:O* rr" pyramidal (rp3 hybrklscd)
whereas NOr- rnd BIr3 arc triaugllar
planar
Thus CO ontains kjpie bond, CO.
1.rp2 coarairrs
N is tincarl doublc bond $,hile C)O32- contaiDs
between single
]I d()ublc hond Hcnce C_O bonrl
:nd lengths \!.ill
C' De |l1 lhe order :
. , /
.CI V co<co2<co32_
r 41. tt (ttz0) = 1 84 D, ir (\Hr) -
11 sol
I .4,., D. I1 and
CI are less polar and heDce will
h ve less dipolo
cl moment.
",
= I 7r2ril.ls\oi 6( cs is 2.2, rhc
\y
uith sante
are calhd
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6182
arolioearsp€ctes
isGstrudural. BothXeFzandIF;
(] _cl
(l
\
ctl",. 'ct
s3, : o: CC14 (synnnetrical)
(2 bond Pairs and S lone Pairs)
,,'\- :r: tt=0
:I': 60, No. of olectrons in NOt =? +24 +1=32
No- of elsctrons in C4- =n * 24 + 2 - 32
=5+6x3+l=24
AR
otI
rl 'lotal no, oIvalencc electrons in COl-
C
-lLnx3+2=24
spz sP-
N
o d is trc-1!cr thallthatfor
61.
"'' il;#'t1'-
Bond eDcrg-Y
6'j66 is
's = 264 kJ uol-r)-
11 = ra? kJ
i.,of -, ,o.r fo,
\aith a bord angle
62. A1l of thcnl arc lriangular planar
'fhere is l,lo co-ordinate bo[d' ot t20". .__ . .-F-
6J, nforO=(:=O lnd 1...-s,\1, tt
t No ofT-bonds=s-
@ NO, and Oa are beDl nloleculeii
uith perna[cDt
structure and therc-
5t.
- Ib ) is symmetrical wirh linear diPole rnoment
ioi., ritt hr," ,"ro diPole moment'
64. both have oPen book tYPe struc-
59.
/47) They howcver ciilter i[
bond
lengths'
"\/"
n.+.+'c'<+Rz
"\ */\,
H/
cH3Ct
ctla (Symmetrical) sruclu re.s
(Bond moments
C -H, C-Cl reinfor'e
rc giw rtsultatrt Rl 120'
Hencc ON
Res$ltaflt Rz further adds uP)
7r=186D
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CHEMICAL BOND!NG AND MOLECULAR
STRUCTUBE
6/83
NOz+ h s no uDshared elecrror and 71.
ry hybridisa-
tr('r) Ilulrceshapcisllnear{O
= N _ Ci; wrrtr bond
irn$le = lx0.
NOz hts onc unshared electron rr.hereas
NO, has
one unsharcd elecfon pair. I{cDce iD NO2-,
the
rcpulsx)n on thc bond pcirs are olore and
anglc is
Icss
69. Similar roCtIi, discussed or page 6/44. 77, HF ts-lcilst voliltrlc duc ILJ sLrong hvdro-ten b( rochng
70. H2S < NH3 < siH4 < BFI 7& In NIlt. oclcr ol N is contplclc. Ilcn(c
C
rt is not
92.6" tor u,
S
{w 12n"
electron deficicnt
N
IA
IIT
ADDITIONAL AESTTONS
As s erti on-Re a s o n Ty p e e.u e sii,lio n s
Thequestiotrsgiven belotd coDsist
ofan .Assertion, in column
key to choose the sppropriaie otr6iur r. 2. Use the following
(a) Ifboth assertion and reason
sre coRRECT ard reasor is
(6) Ifboth assertion a,,d reason are C.RRECT the coRREcr expranalion ofthe assertion.
(c) If{ssertion is CORRECT
but reason is not ii" a"o**""ar.-rrratioD ofthe asscrtioh.
but the reason is INCORRECT.
(d) Ifboth assertion and reason are INCORRECT,
t.
e shared parrs of elect#epel
each olhcr wjlh eouat
ce so rhar al bonds are
equidisranr li._.;.;.;;;-",
randon)
nsofelectrons arouDd
nucleus electric dipolc. which
ces a rra
in lhe nearbJ,a(onts.
+
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6184
Pradeep's
Assertion
3. The nearty tctrah lnice, each watsr molccu-le
lorms four hydrogen bonds as
about the q,rygen each nrolecule is fixed in spaca.
to form hydrogen
bourin! water molecules.
Ttere ire ten valence electrons on sulPhur aiom in The structure of SF4 molecule is a distorted trigonal
SF4 molecule. bitryramid.
BF3 molecule is planar whlle NF3 is pyramidal' N atom is sntaller than ll
occurs in p-Nitro-
6. o-Nitrophenol has a hiSher boiling poiot thaD P- Intramolecular hydroge[ bonding
N itroDhenol. phe[ol.
7. lonic'compounds tend to be non-volaiile' The intermolecular forces in these compounds arc weak'
(A.LI.M.S. 1994',)
polar mvalcnt molecule, the shared electrons sPend
The atoms in a covalent molecule are said to share tn a
electrons, yet some c{valent molecules are Polar' more time than average near one ofthc atoms-
(A.I.LM.S. 1996)
N in in NFI3 has,ty' hybridizatior'
NOt has ,'P2 and
NO3- is planDar while NHr is Plramidal'
(A.I.I.M.S. 1997)
t Electronegativity of phosphorus atom is less than that ot
10. Tbe bond angle of PBr 3 is Sreater than that of Pl-I3 bu
bond aogle of NBr3 is less than that of NH3
nitrogeo. 6.1'I'M'S' 1998)
11. Tbc diPole moment helF to Predict whether a The diPole n]onlent helps to Predicl the teoDletry of
molecules. Q4 LI M'S' 1999)
molecule is Polar or non-Polar. R
'IIe lone pair-lone pair rePulsioD is weaker thaD boDd
,2. All F-S-F a;81€s in SF4 8re Srester thar 9e bu t less
EE
pair-bond pair repuliion. 6'I'I'M S' 2004)
thao l8(f.
AR
True/False ?talements
C
ing slateme s :
all its outer electrons.
IA
,trtls thc
iXiiiiiilr.iiil.:,
R
EE
AR
C
S
N
IA
IIT
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AJN[T
Eq.rilibrir-l rn-!
(Equilibrium processes & phase
Equilibria)
categories : "ru._
$-Those reactions which proceed almost to
completion r.e. concentrations oi tfr" ,!u"tr"t.
is negfuible.
f"ft
t(d) Those reactions in which only a small
equili[du, may be define mis
Ii,:l
..
(ufThose reactions which proceed to
such aa
eKent that the concentrations of the,"u"tuit..
products at equilibrium are comparable.
_a
which
are in
es ofth
7t7
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PradeeP's
712
/.2. Equilibria
TO VACUUM
Thc dilfercnt typcs o[ equilibrir irrvolving PUMP
are
nrrr.i.ri .ttrng"t ulongvirh suillhlc cxamples
Lricfly described ['elow :
of
ir) solia-Liqula ,'(-
,."t. tt:.oi" i.".ub.. ulo n
VACUUM
,,n.t nntrnrt atmosPheric ,r leavc rhc
a
"onnected
rn"* f". and addition of liquid into it'
S
.i""- ""**,i"n
i. Fig T l Supposc the vosscl is llrst
N
""**i..r.
i ii. ,rnorn.r", *ill be samc' Norv supposc wul cr
IIT
,t,. apParirl us rs
and the wholc
l. oJa"U ;r,l'o
,if.*"a ,o stay at room temPeraturc (or at
"sscl thc
ffii:;
chanqes inlo vapours' lhc iamc
amount o[ wutcr
(u
il;:;; ;i;'s" b'ck into thu liquid wurur
Thus I ctiuilibrium
ni'o.".. *tt.aL"t""satiorr )
I rr" 9-1"1i1$1q"
: Rato of condcnsationl
as
The cquilibrium is rePresented
HrO o s -: HrO k)
in thc
Thc differenr:c in thc levels of rlercury
ttutl f ir'i.'gi".-tt'" cquilihritnt t'trltat ptts;tut ol
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EQUILIBRIUIV
- I
UNDISSOLVED
SUGAR
Tie amounl o! lhe solitl in gmms thnt dissolyes in ln the sealed soda water bottle, the pressure
lW) g of lhc solvcnt to fonn a sotunrteil solution a!
R
of the gas is very high above the liquid, so the mass
EE
( Wrti{altr ofthe CO, gas dissolved is also high. As soon as the
that .roW in
AR
oJ o gas in o liquid rur.lerprcs tcin u cktscdve:-sci). i.e. the dissolved gas escapes out..
S
N
The mt^at ol tt
go:t di\solved in a given nuss of a (i) In liquid <r gas equilibrium,lre
soltvnt ct ar! kmperqture is direoll! proporlional pressure oJ the vapoun above the liquid (i.e. vapour
to lhe plA$we of the glJs above the solvent. pressure) is conston! at constant temperature.
i,e mdp 0r m=kp (u) In solid <------s solution equilibrium,
t+h$c k is acon$unt ojpmportionuw qnd is culled lhe solubility ol the solid in the solution is constant
Iisnr!'s 6fltL\ltnl lts t ob.e depetdt awn thc nature at constant temperature.
oJ the y-s, rulure o! the liquid and tampcralure.
(rv) In gas
Altemdti,el), as the mass of thc gas clissolved
1=i solution equilibrium, dre
mass of the gas dissolved is constant fot constant
corresponds to the concentration ol the ttas in the equilibrium pressure at constant temperature.
PEYSICAL EQUILIBRIA
| 1. If
ol iod.ine is stined in
0.200 g
100 t
K till equilibnunt is reached,
298
what will be the mass of iod.ine found in solution and
the tnass that is lefi wrd,issolved. After equilibium is
reached, with 0.200 g of iodine atd 100 cm3 of wate4
ll, (aq)l at equilibium =0.0011 inot L-1 at 298 K
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714
Pradecy's New Colrge
Solution. As the solubility of iodine (con- . ExAIlt'LE 3. Fill in the blsnl$ (a to i) in the
ccnlration et cquilihrium) is 00011 mol L-' lollowinE, table which contains the solubility thta of
(Cive o), Lhis mcans thf,l at equi!ibrium, oxygen in wotet o! 299 K.
1ffi0 cm3 of water dissolve I, :0.0011 mole EpL [o2@] Lo2 @q)lcq.
: 0,0011 x 254 g lnol L-l wd; ..1
(. Nlolar mass of Iz = 254gmol-l) I 106.4 a 0 0012 b
c 0.080 d 0 029
= 0.24 e
0.2i194 e = 0.li 0 029
333.3 e
. . 100 cm3 ofwater dissolve I, = 0.02E B
M 46.1 f 0 0a53
.. l, Ielt urrdissolved = 0.200-0.024 V 598.8 i o o28
_ o.til c (N.C.E.R.T.)
On adding 150 cm3 of water to the above Solution. Expt. I.
soluiion. total volume ofwater : 250 cm3. As total
solubilitr.rt iodine is 0.28 g L-1, therefore iodine PV : nRT or P=+Rr=cRr
that rvill disr,olve in 250 cm3 of water (
= ffi"250g= 0.076* o, C=+
106.4 kPa
.. I, lcft undissolved = 0.200-0.070 g - r;
(8 314 kPa L KjTlnol-l; 1zw
= 0.130 I = 0 043 mol L*r
Molar concentration of the solution R L-l
EE
i.e. a=0 043mol
0.130
'-- x 1 x lfi)O
= 'j254 ^
. b_o.Wrz=ffi:oozr
AR
250
C
- 0 0011mol L-r n
Il.
S
A" C with COz ql d pressure of 4.0 otu. Late\ the or d = 0'fi)23 mol L-l
IIT
bottle wqs opened qndthe soft dtink allowedto come P: CRT = 0 080 x8 314 x 299
to cquilihiunt at 25' C with dir containinq Cozat a : 198 9 kPa
prcssttrt: of 4'0 x t0-a utm. Find lhe concenlration i.e. c = 198'9 kh
of CO, in the freshly bottled soda ond in the soda
Exnt. IIl. = 0'02e
after it had stood open and come to equilibium. The ol5
Henry's constants Ior oqueous solution of COrare or e =00377 molL-r
At 0'C, k : 7.7 v 1g-2 o1^-1 P
^41-1 Expl.IVf=C=-
At 25'C, k = 3.2 x 1g-2 7-1 os,r-l
^o1 offi' |
Solution. By Henry's law, C = t1r where C is
gas concentration in solution,p is the partial pres-
= 8.3t4 x 299 = o l87 mol L-l
sure of that gas aod k is Henry's constant.
8=
o'?53=ffi =,,.04
(a) For the freshly bottled soft drint
C =kp
= (7.7vLO-2 rrlolL-r atm-1)x(4.0 atm) Expr.v. &=c=+=#*6q
:0 30E mol L-t
=0 241 mol L-l
(b) For opened soft drink at equiJibrium with
atmospheric CO2, 1= o.ox
h
C = (3.2x 10-2 mol L-r atm-1) x(4.0x 10-a atm)
= 1 2t x 10-s mol L-l .'. i=O'A)BxO'241 = 0 0067 molL-r
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FQUILIBRIUM
- I
715
If
pieces of gass
Equilibium is d)msmic in nafi.re i.e. there
3. tuDe heated from from
are two opposing processes taking plaCe at equal the other end (F ction
rates. takes place :
1. 4t equilibi,tm, the concentations ofthe dif_ 3 Fe (s) + 4 HrO G) - Fe:Or (s) + aH. (g)
- lnoo
f?ient subslqnces become constant qt constant Stc{m - Ircd odd. Hydrogen
tentpe.rarurc (asexplaioed in equilibria (ii), (iir)
aud
(iu) above) IBON
. .5. At eqdilibium, there eists an expression
--->
involving the concentrutions of the ,rubstancis which
ts constant at constant lempefature.
--+
STEAM
H2
(a)
e.B. for CO, G) -_ CO, (aq), R
EE
lcoz@s)l _>
AR
I
LIJ
C
a single arrow t
It is represented by puttirg
S
N
A+B-+ c+D
A few examples of irreversible reactions are
as follows :
equal. Hence thc reaction has attained chemical cotrstant beciluse the colcentrations o[ H, I, and
,
equilibrium. HI become_constant. Similarly, in the decomposi_
(2) Decomposition ofNro. in a closed vessel. tron ol CaCO3 in a closed vessel at a particular
The decomposition of N2O! in a closed vessel is a temperature, the amount ofCO, becomes constant
reversible reaction as rcprescnted below; and in the dissociation of NrOo at a particular
NzOr G) 2NO2 k)
(Colourlcss)
i_
(Reddish browo)
NrC)n is almost stable at 0"C arrd is almost
colourless. Thus if NrOn is taken in a g;lass bulb
dynamic traturr of
Haber,s proceis,
of N, and H, and
carryrng out the__reaction at a particular tempera-
l.ure, whca equilibrium is a .ained, tbe conc€Etra_
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718
is dynamic in nature.
z
I
kd,
z R
EE
SATURATED
o SUGAR SOL
AR
o
(.) UNDISSOLVEO
d, RADIOACTIVE
C
SUGAR
o
S
N
dYnamic equilibtium'
IIT
more clearlY :
senlzining undissolved
su e dissolved sugar in tbe
;; eakei is tilted so as to does not stoP.
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EQUILIBRIUM I
- 719
:91:our_
NrOo (already discussed in section 7.4.3-) prove the
Contains mostlv No"
above characteristic. (Reddlsh bro,;n) '
o
WATER AT 298K
Ha um
_ fhis is obvious because
lowed to escape
ifaay product is al- 2
out e.g. CO, gas in'cise of decom_
position of CaCOr, the reaction will no loager
remaia reversible. A chemical equilibrium has a
meaDrng only tor a reversible reaction.
Similarly, the reaction is irreversible if one of Nron
the products separates out as solid e.g., Noz
(Colourlci6) (R./di.h broDn)
AgNO3 + KCI ......- agCI +IOI{O3
I whereas the reaction taking place in bulb B
is
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7110
2 NO2 Nzoo
(Rcddishbrown) (Colourless) a*I;nolesflitre
This is the active mass of the given NaOH
solution,
The activc mass of a substance is rsually rep-
rcscnted by putting the formula oI the substance in
Similarly, reconsider the reaction sqnare brackets, Thus in the above case, wc can
write
Ha@) + tz@) + 2HIG)
(colourlcss) (M stands for'Molar'
1c"r.rir"*) fPr.Prcl [NaOH] = aiV"
If 1 mole of H, and 1 mole of I, are taken in
concentration i.e. moleVlitre)
bulb A at 500'C and 2 moles of HI are taken in an
Mathematical exprtsslon. Consider the reac-
identical bulb B at 500" C, the inteD'sity of colour in tion
bulb A decreases while th A+B Products
and ultimatelY both hav '
According lo Law of Mass Action,
colour. This again Proves
be attained from either direction' Rate at which A reacts ( [A]
quitihrium Ratc at which B reacts c. [Bl
"(v't A cattbst ito6 not aUEt lltz state oI
. . Rate at which A and B react together
ZA + 38 --_--.--------+ products
C
It can be written as
S
A+A+B+B+B-Products
N
quiclCY---
IA
Actio n
Rate at which second A reacts d [Al
e two Norwegian . . Rate at which A reacts c. [Al [Al = [A]2
aw concerning the Similarly rate at which B reacts
action on the con- :
s law il known as "t lBl [Bl [B] tBl3
.'. Rate of reaction between A and B
Law of Mass Action. It states as follows :
c( [A], [Bl3
=4
4t)
moles in V Iitres
reversible reaction in equilibrium. For example, Tlu product of the molot conc lrsti Ls of llE
consider the general reversible reaction products, earh raised to lha pover equal lo its
A+B <== C+D stoichiomplrb coeffteicnl dividtd hy the prod.acl oI
lhe molar concpnlralions oI lhc rcdclanlr, eqch
At equilibrium, suppose the active masses of mised lo the power equtl to ils stoichirmelric coef-
A, B, C and D are represented as tal, tnl, [C] and fici.ent is coratunt ql consta lcmletolwe and is
IDlrespectively. App$ing the Law of MassAction, caI&d Equilibrium constant.
Rate at which A and B react together i.e. Rate It is customary to use K" for cquilibrium con-
of the forward reaction c( [Al [B]
stant expressed in tcrms of concentrations. Where
:
ki [A] [Bl there is no doubt that K is in terms ofconcenlration,
c ls omittcd.
where'k; is a constant of proportionality and is
called velocity constant for the forward reaction. Concentration Quotient or Reaction Quotient
and Predicting the dlrcction ofr€actlorn.For the
Similarty, Rate at which C and D react reaalion
together i.e. Rate of the backward reaction aA + bB <-------\ il+/{
c( [c] [D] or an! slage of ht redcliot , o,hsr tfun the stage oI
chemical equilibrium, concentrqti.on ratio given on
= k6 [cl [Dl
the L.H.S. oI eqn. (i) Lt called conrentralion
where ki' represents the velocity co[stant for the quotient ot rctetion qlotienl. It Ls wually repre-
backward reaction. smted by Qor Q. Thus
At equilibrium,
R g, =
IX' tnt
EE
Rate of forward reaction = Rate ofbackward concentr*tion quotient,
reaction V|'IBIb
AR
tcltDl _ k/_ -
(ii) It Q > K, QwiA und to d*re6e so L\ la become
S
_ ci. ci (RT)x
of A, B, X and Y respectively in the reaction mix- + v
ture at equilibrium. It may be noted that the pres-
sures in the above equation are taken in ci. cB (RT)"*o
abnospheres or ban or pascals (in SI units) .
Ci' C{'
- (a + b)
T.TT Relallonshlp between Kp and Kc t:tttii#:iitl:i::i:i:i:::::.i;.:.:.:i: - (RT)G+y)
co' c'"
Consider the general reversible reaction : Iq. (RT)^"
sA+bB =-l xX+yY
ci dt
If the equilibrium constant for this reaction is R
where K"
'- accorcling to equation (i)
q.cg
EE
expressed in terms of concentrations, $re may write
AR
ft
IIT
Hence
where C6, Cg , Cy and Cy represent the molar
concentrations of A, B, X and Y respectively. As the partial pressures are taken in atmos-
pheres, the value of R to be used in the above
If A, B, X and Y are gaseous, the equilibrium
constant for the above reaction may be expressecl
equation will be 0.0821 litre atmospheres/de-
greelmole. Temperature T will, of course, be in
in terms of pressures as
degree Kelvin ("K).
Further, as a.lready mentioned in unit 1 and
"r:m
If the gases are supposed to be ideal, then we
...(,, unit 2,
l pascal, Pa = 1Nm-2 and l- bar = td Pa.
If pressure is expressed in bars,
can apply the ideal gas equation, viz.
R = 0' 0831 litre bar K- I mol- 1.
SOLUED EXAATPLE
KP = 167 at 1073 K.
I.\ns.l.5l x ld stml
IIT
(4Ir^,, =0,Ke= \ (,t) If lr, = +w (i-e. no > n,), K, > K" (ni)IfAlr: -vc(Le.nrcn,),Ko<K"
S
N
IA
lg.clll'llt1qlcjjLElgllEgm constant',
IIT
K= INH:12
(i)l N2+ o, <--------\ 2No
[For reaction
tNrl tHzl3' 2NO + C)2 <- 2NO,
Reversed
IA
1/K
IIT
Divided by 2 raK
Multiplied by 2 K2
DMded into 2 step6 K=Kr x&
(ri) Predi4tinn of the ext€nt ol reactjon. Thc (b) Intermediate value of K (10-3 to 103)
magnitude oJ e4uiubium conslant giyes at idea
the shows that the concenl.rations of the reactants and
ol c rekfiive dmounts ol the readants snd thc products are comparable e.g. for the reaction
producls. Fet+ (aq) + SCN- (aq) <-.-. [Fe(SCN)lr+ (aa),
(g) Large value of the equilibrium constant K" = 138 at 298 K
(> ld) shows that forward reaction isfavourerli.e. (c) Low value ofK (< 10-3) shows that back-
concentration of products is much larger than that ward reaction is favoured r. s. concentratiou ofreac-
ofthe reactants at equilibrium e.g. for the reactions
tanls is much larger than that of the products i.e.
H, (g) + Br, G) .-=) zHBr (g) the reaction proceeds to a very small ext ent e.g. for
4xtore the reaction
L=5
H, (8) + Cl, G) ZHCIG), + O,
N2 G) G) i------\ 2 No G),
KP=40x1dt
----------:
This shows that at equilibrium, concentration
Il = 4 8 x 10-3rat298 K
of the productsi.e. HBr and HClis veryhighi.e. the This shows that a1 equilibrium, the mixture
reactions go almost to completion. contains mainly N, and p, and very little of NO.
i
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7lt6 t )ralta (
r's Neut Coutse Ch"-ittr4rJBII)
(vii) Thc vahr d lhl eqz,l,ilibitnt corrsldn b nnt (S)z : equilibrium constant at
affrteilby the aihlition oI a calalysl b tke ruulion. tempcrature T2
activation for the forfrard and backward reairtioiis I : rn which the number of m<rles of
Tlpe
are different, so a given hcroase i.n temper atur-e wiu ptuducts is cqual to the number of moles of rcactanlti
iucrease the rate of the forward and backward l7 +
}j.z+ zt{l
reactions to different edents. In other words, the
values of the velocity constants for forward and N"+Oz <.- 2NO
backward reactions i-e. kl ardk6 will change dif- CCI + HzO COz + Hz
ferently with a given rise or fall in temperaturc. R i--
EE
hrrther since K = k/kt,therefore, the value of the [pe U : m which the number oI moles oI
pruducts is not equol to the number of moles oI
AR
reacaorrts
C
N2 + 3H2 . ^ 2NH3
S
N
2soz + 02 2SO3
IA
PCls \-
than t5) and that of an exothermic reaction
decreases (k, increases more il!i" k/ with rise in
\or 2NO.
teEDerature. For reactions having zero heat of Two common examples of the reactions in the
reaition, temperature has no effect on the value of liquid phase arc
K. CH3COOH + CTHsOH \-=
Quattitatively, the effect of teEPerature on cH3cooqHs + HzO
the equilibrium constaot is given by van't HofI
equntlon, viz. Fe3+(aq)+(SCN) -(aq) <- [Fe(SCN)]2+ (aq)
dlnK,
_ AH. (ii) Heterogeneous Equilibria :
-A- - RT2 When in an equilibriumreacliory lhe rdrck nls ond
where AH' is the standard enthalpy change of the lht produt$ are presenl in ttPo or nnre than two
reactioE or in the lDtcgrrtcd form, it may be written phiros, it is caM a heterogeneous equilibrlum.
as (assuming AH' to be constant in the temperatu re
A ferv common examples are as follows :
range T1 to T,
CaC{\ (s) Cao (s) + Co2 G)
$
(&), aH' (r, - r' )
,be6i;=rmt 3Fc (s) + 4HrO (g) '- r FerO. (s) + 4H, G)
:
[-In ] C (.r) + Hro (8) + Co W) + H2 (s)
where (Ko)1 equilibrium constant at
temperature Tt Water gas
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EOUILIBBIUM I
- 7117
7.'11. Writing Expression tor Equilibrium
(lri) For the reaction
In Hiting
NrOr G) .- 2NO2 G)
(s)l = t and
[CaCO, (s)] = I
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7118
. Ne.4 Course
7.'l2. Unirs ol Equilibrium Constant ,rii:,,,i:i:j.i.iit :;:i::i','-i:.: ::
Hence K = [CO, G)l
Since the concentration of a gas is usually For the general reaction
expressed ia terms of partial pressures, hence we aA+bB # rX +yY
better write Y1= pco,
k - txf IYI: - tmot t-- I l'l'"
This explains why pressure of CO, becomes
constant when equilibrium is attained in the
decomposition of CaCO, in a closed vessel. = (mol L-1)(r+))-(a+6) = (mol L-r)^'r
(ii) For the reaction ,, f* P\ (atm)'+l or
-- lbar)'a/
Kr=
3Fe (s) + 4[LO G) + FerOa (s) + 4H2 G) foq=Gtn,f'-? i5;d.'r-6
Applying the law of chemical equilibrium, we = (atm or bar)(r+/)-(a+b) = (atm)& or (bar)&
have Evidently if &r = 0 i.e. number of moles of
[Fe, on (s)] [H, @)f products = number of moles of rcactants, \ or
-- -
^' [Fe (r)P tH,o G)]1 K, will have no units.
But by convention, we put [Fe3O4 (s)] = land For example, in case of reactions
[Fe (s)] = 1
Hz G) + Iz G) s--------r 2HI k)
lH, (s)ln
Hence K = or N, G) + 02 G) . ---' 2 NO (S)
lHpGil?
I! or K, will have no units (as n, = n,i.e. Ln = 0)
presr*"*, 5 = P*ro R
EE
or in terms of |fl' For the reaction
AR
as
n"
S
P
K,, = K" has the units (mol L-t1-z and K, has the
N
equi-
= c,5 ,x ,o=
2.3810-a librium will be
= z'qz
C
PCl, = 96-o1"
IA
Ct = 0'8 mole
IIT
[
.. 1 mole of pCl, on dissociation gives
1 mole of pCl, and I mole of Clrl
lo_lC!&n. The reactioa betweeu H, and I,
may be represented as
. Since the volumeofthe vessel is2litres, there-
lore, l.he molar concentrations at equilibrium wilJ
be
H2+ 12 . - 2H.1
*= o.6nort-t
Amounts of Hr, I, and HI at equilibrium are lPclsl =
given to be
H, = 0.45 mole, I, : 0.39 mole tPcl3l =T=0.4molL-l
and HI = 3.0 mole and
Suppose the volume of the vessel (i. e. reaction
fcLl = 9j=
2' o.4mol;--r
mixture) = V litres.
_ |pply,ng tne law of chemical equilibrium to
the dissociation equilibrium, we get
Then the molar concentrations at equilibrium
will be [Chl 0.4 x (].4
,. - -[PCI3]
"" tPal.l =1" = 0'267
tH,l= Y,r,,l = Y K, = r! (m)&
and [HIl = $ noteVlitre Here An:no_ nt=2_l=7
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j'rtt tla c t,' -< Nert Course Chemistr4frft[)
7l2O
s=
K"(Rr) or
0'1-x
But T = 327 + 273 = 600 K (Given)
or f+ 0'0414; - o'00414 = o
R : 0.0821 litre atmosphere/degee/mole
.. \ -- o%1 x 0.0821 x 600 = 13'15 l V16 o+l+12 -ax t tr1-!'m111
x = -0.0414
, l, \ \\ll'1.1. 5, For the reaction, 2_
b !!b2-4ac 1
the formula *= )
[Usin8
-0 0414 * y'6 --i-
mr-+-oT656-
-
-2
o'M14 + 0 0182b
Solution. The reaction is -2-
ffi+rHr61 .- 2NH3G)
=z-0 0414t 0 135
pressure of 1 atm)
1H3COOCS{s(l) + HrO (t)
N
..
K, =
4I" E = oao ire:aY -= "" " (d) Starling with I 00
IIT
dis
"q"iti\;"^,
sociation ol PCltis 0'0414'
of Clt at
$plullo". Suppose the concentration
equilibrium isx moles/litre. Then we will have Solution. (a)
PCls + PCl3 + clz
0 cH3cooH + ql{5oH <- C}{3COOC2IJ{ +HzO
conc. 0.1molo
Initial 0
..Totalpressure ar cquilibrium
= 500 -p + p + p = 500 +i, mm
500+p= 700 (Given) or p = 200mm
und,thc ..(utccntration ofAg+ ions is J.U Hence at equilibrium
x l0 -q ntol
L- 1.
ls this system ot
equitibiunr ? pas, = 500 - 2ff) = 3ff) mm,
Solrrti-on. Applying the law of chemical R
,., r:qui_ 2o, = 200 mm, Zs = 200 mm
EE
lrhrtum to the given roactjon, we have
Po! tr& 2oo-x-2oo
AR
Peo2-
C\2+ (aq\l lAs (silz K, =
K: ' 300 = r33.J mm
[cu(s)l [Ag+ (a4)1,
C
*r1".
S
rre
l5d_ = t). r7E.
*_ lCur+ (cq) I
atmosPheic Pres'
xrrPPa=o 4x105Pa
100
S
QxrotP,
N
which it will be
stue is 0 2. Calculate the pressure at ' Partial Pressure ot lz (plr) = fOO
IA
7 /23
Thking square root of both sides, we get
. If total mass of the nixture of CO
P7 and g, then
,Od-pt=4xtd
or 4x702p=2(7O-p) CO = 90.55 g and CO, : 190_90.t5 : g.45 e
or .'. Number of moles of CC) = gO.55lZA :
4O2 p = 26 3.134
20
Number of moles of COz : g.45144 : O.Zt5
ot p=
m= 4.,)8 x l0-2 bar .
' ' Pco =
3.234
xI
Hence at equilibrium iajiTd7ia arm = 0. 938 arm
R
EE
AR
C
S
N
IA
IIT
I \ri. (a) = 2.0 x 10-3 mol lit-l (D)=2oxrot5 llz(9+tzg) + 2I{I(8)is5a 8. Ifo 5nrol
(c) = 3.t6 x 1o-e mol lit-li L-l of HI G) is present at equilibriuul at 700 K,
11. WheD PCl5 is heatcd rn a closed vcsselat 575 K,lbe
what are the cencentrutions of lI2 G) aDd I2 G)
rs found to be 1 alnr
assuming that wc lnitially started wilh Hl (8) and
tolal pressure at equilibrium
and partiai pressure of Cl2 is fourrd 1o thc 0 324 allowed it to reach equilibriunr at 700 K.
alm. Calculate the equilibrium constaot (Kp) for (N.C.E.R.T) [ r,r,i [H2l = [I2l = 0 068 mol L-ll
the dec{mposition rcactiou. [.rns.0 29t1 lll. 'lle equilibrium consiaot for the reaction
12. In lhe dissociaiion of Hl, 20% HI is dissociatcd at CH3COOH + qHjOH <-\
equilibrium at a certain terirperaturc. Calculate
CH3COoC2FI5 + Hzo
Kp for the reaction
is R
4 0 at 25"C. C-alculate the weiSht ot ethylacetatc
HI(s) <-
EE
lnr@*!rr@1. that will be obtained when 120 g oL acetic acid arc
[,\t'\ Kp=K.=01251 reacted with 928ofalcohol. [.\ll3 f17'048]
AR
13, A reaction mixture containing N2 at 0 50 atnl. t9. A sample of pure PCI-5 was introduce.l into an
C
I
or ai=l+3-4x
= 5---0.525 0.525
AR
=0 975
0.525 or 3l+4r-3=0
^..._----_-zrT-
C
v _(o.525/g@.525/4\
N
= 0.465 mole
New inirialconc. of Cl2 6. Suppose-we sta( with I
= 0.10 + O.l0 n]ole of HI and.r is the
oegrce ol d,ssocialion. Then at equilibrium,
= 0 .20 mol L-r lHIl = (1 -j)A4 tHrl -, / 2v.
New initialcoDcs. of pcl3 and pcl5 remain
thesame
[I2l = x./ 2V moles per lirre.
Supposing -r mole of pcl3 reacls, the
new equF Put thevalues in the equation
librium concs. wi be
[pcl3] = 0.20 _ r,
tHrl [Izl
[Cl2] = o 20 - j and lpctsl = 0.,t0 + x ti= -IHII-
Putting the vatues iD rq=
aDd calqJlate r.
di$, 7. z NU, ,_____. N2 3H2
Initial I mole
iD.to:r(o:i6=, = 20 Al. eqm- (1-{).2) mole
or (0 40 +r) = 20 (0.04 +r2 _ 0.40x) 0.1 mote 0.30 mole
= 0.8 mole
or 2Ol- 9r+0.40=0 Note that 2molesof NH3 dissociate
to form 1 mole
o,*-'t=Elf,i t.
ofN2 and 3 motes of H2.
pctj pCI3 +
t y'ET:ZT)olT:r
- -------2-x-Zn- =o-,
y
Initial -+ clz
a mole
40
At.egm. (a--{.1) I
0. 0.1 mot L-I
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PradeeY's
7126
IDitial
R
EE
I mole At equilibrium, [HIl =0 5 mol.L-1'
1-0 20 0 10 mole 0.10 mole
At. eqm.
AR
IHrl=tlzl=rmolL-r
= 0 80 mole
K=6+=fito*"'l'
C
= o. t25,
S
K"=
N
= 2nrot
IIT
=ffi=";7'=o*'
H3 r,2r (0.50)2 crHroH =!|mol =2mor
- r)n/ mol L-l
At equilibrium ICH3COOHI = (2
As Kp < < Q, reactionwillSo iD the back'vard direc-
Y
lqHsOHl = Q' - x) / molL-1'
tion.
14. 2N2G) + o2G) + 2N2o (8)
lCH3COOqH5l = [Hro] =
t/V mol L-l
lDitial mol 0 933 mol
0 482
K= X*xr= 4(Given).
At eqm. O'482-I o'933-xn x x)'12 -
o 482 -x O933-x'2 x This givesx = 1 33 mol
Molar conc. l0 . . Mass of ethYl acetate = 1 33 x 88
111 o4E
0 x 10-37 is -m--
=
As K = 2-- very small' this means.that
urouot ot l'1, nod 02 reacted ('t) is veryiery (Molar mass of CH3COOQH5 = 88 n:ol-1;
g
,i"
small. Hence at equilibrium, we have 19. Similar to Problem.lT'
+ cl2 g)
[N2l = 0 0482 mol L-1' 20' G) <----\
2 Brcl Br2 GI)
lo2l =0 0933molL-r,1XrO1
=O t' Initial 3 30 x 10-3 molL-l
At eqm. (3 30 x 1o-3 -l)
xD xD
Iq= (x/2\U/2\
v.'c= ----)----------' = 32 (Given)
(3 30 x l0-r -r)'
- z.o x to-31 (Giten)
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EQUILIBRIUM
- I
7127
* .. At eqrD.
4 (3.30 x l0-r -r) lBrcll = (3.30 x lo-3 - 3 0 x 10-3)
= \/fr = 0 30 x 1o-3 = 3.0 x 10-a n:ol L-l
2 (3.30 x 10-3 -.q
=5 66
,,. o.
-c=,!T']J,T4:- o 2e' tr lg)1 =s.ao
,
= ll 32(3.30 x -r) '10-3 [cH4l lHrslz 1.07 x (l 20)'
ot -=JZ
12 32x = 11 32x3.30x 10-3 ,
tu Q" I(", equilibriunt will go in the backward
direction.
or x=30x10-3
sure and temperature is prcdicted with the help of gas (like nitrogen, helium, argon etc.) will not
a principle known as Le Chatelier's principle, change the molar concentrations of the reactants
C
described in the next section. The effect of adding and products. Henc€ the state of equitibrium will
S
remain unaffected.
N
?
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7128 Pradeep's
of adding more of C and D to the reaction in iibiium will shift in thc forward direction. Similarly,
S
backward direction.
tcl or [D] shifts the equilibrium in tbe lbrward
IA
tion in equilibrium can be very easily seen in the dustrial processes because i[ the product is
laboratory with the help of the following reaction reovered iide by side, the equilibrium will shift in
Fe3- (a4) + (scN)- (aq): [Fe(SCN)2+l (aq) the tbrward direction to form rnore product. Thc
(fate yeitoorl (Crlourl..ss) (Rcddish broq'r) removal of product is especially easy if it is a gas.
i.e. if to the solution ofa ferric salt e.g. ferric nitrate For example,
of sulPhocYanide (i) in the manufacture of NH. by Haber's
less) is added, a
proccss, NH, gas is liquehed and hcnce removed
due to the forma-
tion offerric sulphocyanide complex ion. Now if to side by side tiom thc reaction mixture.
t solution or Potas- (li) In the manufacture of quick lime (Cao),
s added, the colour by clecomposition of CaCO3, thc gaseous CO,
showing the forma- which is one of the products is allowed to escape.
Looking at eqn. (ii), it may be noticed that
continuous removal of the product kceps the value
rrf (). Iess than K.. As a rcsult, the rcaction con-
tinucs to move in the forward direct ion
Some examples from everyday life. If in a
system in couilibrium, the
part is disturbed. it no I
NaF mav bc added to the reaction mixture lt com- Iibrium and rcadiusts its
bioes wiih thc ferric ions as follows :
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EOUILIBRIUM
- I
7129
co, G) + HzO HrCO, (aq) thc side that absorhs hcat l.r,. in lhr. h.rckrval tlir.i
S
As partial pressure of CO, is high in thc tis- (ii) .Again, consider thc cndothermic r cirction
IIT
sues, CO, dissolves in the blood. In the lungs, as N2 k)+o2 G) -- 2NO (q), AH= + 180.7 k.r
partial pressurc of CO, is low, it is released lrom or it may be written as
the blood.
cndo
(v) Tooth decayby slrseh. Our teeth are coated N, G) + o, (Jt) + 180.7 k.t s_ 2 NO k)
with an enamel of an insoluble substance known as
hvdrorypatite, Ca. (POo). (OH). It exists in equi- Ob\.iously, herc the fonvard reaction is cn-
librium with its ions as follows :- dothermic whcreas thq backtvard roaction is cx-
othermic. Arguing as beforc, thc incroase ol
Deftineralisation
temperaturc rvill favrrur the [orward reaction whilc
Ca. (Poo), (oH) (s) -- thc decrease ol temperar,ure \vill lavour the back-
R€annemlisation
ward reaction. Thus in gencral,
5 ca2+ + 3po:- + oH-
The forward reaction involving dissocation is
callcd demineralization and the backward reaction :tr:il;;
involving tbrrnation is called remineralization. If we
do not brush our teeth after eiiting sweets, the sugar (3) Effect of change of pressure, This fuctor
gets lcrmertcd or the tceth to produce H+ ions has u.signiliclrnt role to pluy only in r.asc ol guscous
rvhich combine with tbe OH- ions shifting the rcuctions .rnd thosc loo which procecd with r
equilibrium in the forward directiou therebyiaus_ change in thc number o[ moles.
iug tooth decay. (i) Consider the dissociation oI NrO, into
Thus in general, NO-;
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Pradeep's
7130
reaction quotient is
IA
4 moles
1 [NH3l2 t --
IIT
{2 tr',{HJ}'
Q"= =?1N,1
{2 tNrl} {2 tHrl}3 1H7=;r'"
Thus Q" is tess than K,. To re-establish the
equilibrium Q"will increase till it becomes equal to
\. This can happen only if [NHrl increases and
place i.e., in tavour of formation of ammonia. Thus, shift in
'higher
the pressure, the better would be the yield [N2l and [Hrl decrease i.e. equilibrium will
of ammonia. the forward direction.
If,
system
that dir
moles occurs i.e., in the backward direction' In
other words, a decrease in pressure will favour the
dissociation of NH, hto N2 and H2. For example, for the reaction
(iii) Lastly, coosider the following equilibrium C(s)+ork) cl zcoG)'
reaction involving tbe formation of hydrogen
'""*.it" a"=ffii1
iodide.
H, (g) + I, (g) a.l zHr (g)
1 mole 1 mole
2 molcs ElIect ofchange in volume. If the volume of a
gaseous reaction is decreased, the pressure exerted
This reaction takes place in either dirsction
6v the molecules will increase Thus the effect of
without change in number of moles. So according
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EQUILIBBIUM _ I
7131
@@ o =N2
, & 88 @ =Hz
*lq
--#
Q =Hr.
m state. Therefore,
make the process
rature of 750 K is
the leld of NHr, of
course, is less than that at a lower temperature. But
from indusrry poi.ot of view, it is rathei advisible to (ii) Efrect oI tuessure. In this equilibrium reac_
get a poorer yie.ld than to waste time unnecessarily. .
tion, no change in nunrber of moies takes place
Fhely divided iron since one mole of N, combines with one mdle of
achieve the equilibrium r 02 to produce 2 moles ofNO. Hence pressure has
(promoter) is used to incr
no effect on this equilibriuo reaction.
catalyst.
(ii) . (ii) Effeuof Conceatralion. Ahigfcancentra_
ol pressure. It has already been dis-
ffict
cussed above that higher the pressure, gr€ater tion of N, and O, will favour thc formition ofnitric
odde.
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7132
l'ra I t, a y's NeQ Couqle Ch'e',miiitrqlfrlD
Process). The equilibrirrm rcaction involving the CO, and Hl is favoured by high conccntration of
oxidation of sulphur clioxicle to srtlyhur trioxide water gas as well as steam'
may tre representetl as : S
Itigh pre,rxre. Usually, a pressure of 1'5 to 1'7 at- tends to I,he right, i.e' on
C
ccnLrition of SO, and 02, greator lvould be the (ii) Water'Vapour equilibrium -Vaporisa-
IA
tion of water
-e
IIT
yiclcl ol SOr.
4. Brlsch Process lilr the Manulacture of \lhtcr * HeaL <-^ Water vaPour
Less volttnte Morc volunte
Hydrogen. In this pr()cess, H, is produced fiom
Thc change of water to rvater vapour is a
water gas and stcan according to thc following reversible endothermic (heat absorbing) process'
equilibrium reaction: The reaction involves increase in volume i'e' whcrl
H,k) +Cote) +H2ok) = ^ water vaporises into rvater vapour, "'olumc in-
---.-v--Water
Steanr
gas
creases. H"nc" according to Le Chatelier's prin-
ciple,
3 nroles (a) On increasing the pressure on this system
in cquiiibrium, the equilibrium tends to shift in a
: direition in which the volume decreases i'e' eqtli-
,2Hr(8) + Coz G),; AH + 42'0 k'l
librium shitts towards condensirtion of watcr
3 nroles vapour into water. In other words, the increase in
p.tt.t.tt" favours the condensation of water vapoul'
(i) Effcct of Tbnryerurure' The fr-rrward reac-
into u'ater and clccreasing prossure favottrs
tion Ueirig enclothermic is favoured by high vaporisation of rvater into water vapour'
tcmperatuie. Ustrally a tcmperatur e of' 67 3-7 23 K
(b
is used.
vapour
(ii) Efl'ect of Pre,ssure. Since thcre is no change
tcmPer
in tlrgtota"Lno.[',.. of moles in this revsrsible reac- on incr
tion,l.zz.r.stirz llus rut eJJ'cct ot this equilibrium reac-
into watet vapour.
Lion.
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EQUILIBRIUM _ I
7133
(iii) Solubility of Substances. Certain salts sure is
like solve with the absorp- piston,
tion The solubility of suih refore,
salts in temperature. means
On the other hand, certain salts like sodium that.increase of pressure increases the solubility of
hydroxide, calcium acetate etc. which dissolve with gas in liquids while decrease in pressure lowers it.
the evolution of heat, will have lower solubility at For example, an aerated soda water bottle like
higher temperatures. Campa, Thums up etc., on opening bubbles out
(iv) Gas-Solution System. Suppose there ex- dissolved carbon dioxide as pre.su.Jis decreased.
ists an equilibrium between a gas and its solution in
::l;:::::::r::::i:::::::::::::ii::::::::::::::j:ii;i:l::il:::l:::j:::::i::i:ri.i:::::::::::::::::rr:r::j::;:::::::j
dlnK, AIl"
7r- - *7
Assuming aH' to be coDstal)t over a smatl temperature range, integration of the above equation gives
10,,ry=l*B,, R
EE
)
on. I a-r
AR
-"--J
," =
C
or lnKr:-#*,
S
N
= - AI{',2 R.
ii:;i:'i 2. From the van't Hoff equation,
, _Kz AH /Tz-Tr)
,oB
Rr Z:30tR we may conclude that
(r) rf
t-rtj,
= 0 r.e. no heat is evolved or absorbed in the rea tion,
^H log (K2lKt) : 0
i.e. K2/\ 1
or IQ=Kr
i.e. equilibium. conttant does not change wilh tem.perature
C'o
i , I::::t
N ue-str..iQna
:::ll::ll;i i:::l:ilitiiii:::::i::::::ll::::::l::li!lit::::ilii:i::::::::iii::il::ili::i:i::::::i
if any, do you
sugar is addetl into a saturated solution of sugar in a beaker- what process/processes
' L some
Q.
expect tJhappen with the passage of time? yghat is this state called ?
take place at equal rates. It is called a state
Ans. Ttro proceses namely dissolution and precipitation will continue to
of equilibrium.
1j - Why gas fizzes out when soda water bottle is opened ?
pressure' On opening the bottle, the pressure tends
Ans. The amount of the gas dissolved is very high due to high
to decrease to atmospheric pressure. Sb th1 solubility decreases i'e' the dissolved gas escapes out'
between acetic acid and ethyl alcohol attains a state of equilibrium in
an open vessel but
- -r, Reaction
e.
decomposition of CaCO, does nol T[h]?
and water are also liquids but one of
Ans. Acetic acid and ethyl alcohol are liquirls and their produ_cts ethJl acetate
the products of Oecomposition of iCO, is gaseous (COr) which escapes out and the reverse reaction cannot
occur.
and pr.oducG remains constatrL Does it mean that the
e. 4. At equilibrium, the mass of each of the r.eactants
reaction has stoPPed ? ExPlain.
wall as backrrard directions but at
Ans. No, the reaction does not stop. It continues to take place in the fonuard
as
equal sPeeds.
Q.5.Whathappenstoareversiblereactlonifocatalystisarldedtoit?
both the rate of forward and backward
Ans. The state of equilibrium is not disturbed but is attained quickly because
reaction increase to the same extent.
cylinder litted witn an air tight piston contains a small aDount of a liquirl at a fixed temperature' The
- 7. Apiston
e.
is moved out so that the volume increases'
C
(D) Hor witl the ratcs of evaporation and condensation change initially ?
IA
(N.c.D.R.T')
(s)12
Ans. (i)K= lNo lclz G)l
,r
lNocl G)'
[NqSoo (8)l ICo2 G)] lcoz G)l Pcoz
(,,) K
1N,pq 1r;1 tsoz G)l lo,itglr/z
(r2NH3G) N2G)+3rr2G)
<- (ii)
; N, G) +
] u, rsy .=,. NH,et
(iri) 2 N2 G) + 6 H2 G)
+ 4 NIt3 G) w.c.E.R.T.l
t-
Ans. (i) Ke = (x) tAT (iii) {a I )r.
(l
41 R
EE
I-1 What doqs the eqrilibrium constart K < I indicate ?
A[s, Thc
AR
Ans. K = kl / kt.ln exothernlic reactlon, with iocrease of ten'rperarure li6 iocreases much nrore than lil. Hencc
K
S
N
decreases.
(.)
IA
I 5. Writc exprcssions for K, nnd K. for the retrction CaCO3 (r) i:. CuO (x) + CO2 G),
IIT
Ans. K" = lrtr*ffig, lirkint acrivc masscs of solids as uniry, q = lco, E)1. sjmi tady Kp = pcoz.
Q: I Explaitr why pure liquids ond sotids are ignored whilc writing the equilihrium colstant exPression.
(N.C.E.R.T)
\o of mol€s= Mass/nrol nrass
Ans. IPure liqurd]or IPure solrdl = ffi;;i t- --fiffi
Asdensiryorapurerio,,..,;,:ffi;,I,ll,,,T.,iln=.,llffH,atureandmolecularmassisarsocoosranr,
thersforc their molar conggntraticDs arc constant and included into the equilibrium constant.
e 22- Whot q nlitative ihformation cnn you obtein from thc msgritude ofequilibrium constoEt ? (N.C.E,R.T)
Ans, (i) Largc value of equilibrium constant (> 103) shows that foruard reaction is favoured t.a coDcentration of
produots is much larger than that of the reactants at equilibrium.
R
EE
(ii) lnterDediate value of K (t0-3 to 103) shows that the co[centration of thc reaotants and products are
comparable.
AR
(iii) Low value of K (< 10 - 3) shows that backward reaction is favoured ia crmcentration of reactants is much
C
Whot will happ€tr if (i) Volume of the reaction vessel is sudde[ly rcduced to half?
(ii) the portiol pr€ssure ofhydrcgetr Ls sudderly douhled ?
tcH,oHl Por.oH
\= p*i4
(i) when volume of the vesselis reduced to half, the conoentration ofeach reactantor Product becomes double
'llus
2 tcH.oHl
o"=
rrcorxffi;F=;K'
As Qc < Kc, equillbrium will shift in the forward direction, producing more of CII3OH to make Qc = Kc'
Por.ox - 1
Q 25 Hydrogen gos is obtoined fmm nfltnral gos by portial oxidation wiih stecm occordiDg to thc tbllowing
cndothermic reaction
CIt4 G) + Hzo G) Co G) +
+ -r H2 (3)
(@) Write lr expression for K, for the above reaction,
(rr) I{orv will thc value of Ko and composition of the cquilibrium mixhtre bc offected }y
(i) increasing the pressure ?
(ii) increflsing the tetnpemture ?
(iii) using a catalysl ?
R tN.C.E.R.T)
EE
Pco x P3y-
Ans. (a)xp =FA,l.r.r
AR
(r) (i)
C
( l) Equiiibriunr conrpositioD wilr not be distu rbed bu t equirib.unr will be ar raincd quickry.
IA
IIT
Q.l.Whichmeastrrablepropertybecomesconstantinwnter
temperature ?
Ans. Vapour Pressure.
Q. 2. Give one exnmple of everytlay life in which there is gas <- solution equilibrium'
furs. soda-water bottle.
Q. 3. Unrler whnt condition, a reversible Process becomes
irreversible ?
Ans. If one of the products (gaseous) is allowecl to escape out (i.a. in open vessel)
Q.4. What happens if ferric snlt is added to the equilibrium of the reaction between [e3* and SCN- ions ?
Ans. Red colour deePens.
Q. 5. Wrat is the effect on the value of equilibrium constant on adding cntalyst ?
Ans. No effect.
Q. 6. Write the expression for equilibrium constant
K, for the reaction
3 Fe (.s) +4 uzO G) + IerOn (s)+4 u2 G)
Ans. K, = pHr/ pH,o.
R
Ans. EquilibriuDt will shift in the forward clirection fornriug more of ammonia'
EE
Q. lt, lurat are the conditions for getting maximttm
yield of NfIr by Haber's process ?
AR
reaction.
N
temperature ?
Ans. No etf'ect.
\ r.t l.l l. What clo you understancl by ternr 'Equilibrium' '? Explain physical equilibrium with one suitable
.
ro 7 -1. exan:ple.
2. Give one exanrple of each ol the following equilibria :
S.Unrjerwhatconciitioneachofthefollowingequilibriacanexist:
(i) Solid-Liquid equilibriunr
(ii) Liquid-gas equ ilibriu m
(lii)Solici-solution equilibriu m
(iu) Gas-solu tion equilibriutlr'
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7139
EOUILIBRIUM
- I
\cr ' 1 6. What do you u[dcrstand by Rerversible aDd Irrcversible reactions ? Iluskate your answer with two
examples. Under what conditions a revcrsible reaction becomes irreversible ?
7. What do you understand by chemrcal equilibrium? ExplaiD with orle suitablo example.
t. What do you understand by dynamic nature of chemical equilibriuD ? Give one experiment to provo
that equilibriunr is qnanrc in nature.
9. List any tbur important characteristiG of a chemical equihbrium.
\,i ri 10. State and explain the Law of Mass Action.
\,( l6 11. State aDd explain the'Law of Chemical Equilibnum.'
12. Derive a Seneral expression for the equilibrium coostant.
i!( r1. 13. Whatdoyou undcrstand try Kc and Kp I Derive a relationship between ihem.
14. Under what conditions Kc K, for a gaseous reaction 'l
=
s!r. 7.s 15. List the importa[t characterlstics ofequilib uD constant.
16. Hou does the magoitude of equilibrium constant give an idea oI the relative an]ounts ol the reactants
aDd products ?
cfi1-
N
=-
(v) CH3 COCH3 (l) a-------r CHTCOCH3 G)
21. Applying the law of chcmical equilibriunr explarn whyvapour pressure ofwater is consrant at coDstaDt
temperature.
5r'c I ll 22. Why strictly speaking equilibrium coDstant has no uoits ?
5, ( .I.1 23, '[he cquilibriun] constant for the reaction.
rrr : ri. 2H2 G) + O2$) + 2H2O (g)
is 1.2 x 10o at 298 K,:a quite Iarge while H2 and 02 do not react under ordinary coDditions. IIow
do you explaio it ?
24. What is theeffect ofaddinga catallst or a reaction which is (a) io equilibrium (b) Dot in equ ilibrium ?
25. What is the cftbct ofaddrng I mole of He (g) to a flask containing SO2, 02 and SOJ iD equilibriunt ar
coDstaDt temperaturc ?
26, Name the factors which iofluenc€ the equilibriunl state. Explain iDflueocc of each tactor with the help
ofexamples.
27. State Le Chatelier's principle. Givc two examplcs of its applications in chemical industries,
2t, The follolving reprcsents a gaseous system at equilibrium.
2SO2 G) + oz G) + 2SO3g)+ Heat
IDdicate the direction in which the equilrbriuD will shift when rhe following changes are nradc :
+ lorO,
IA
(i) Effect of temperature on the solubility of sugar in water, given that dissolution of sugar in water
is an endothern:ic process.
(ir) Effect of temperature and pressure on the solubility of gases in liquids.
(iii) Effect of pressure on the boiling point of a liquid.
(iv) Effect of pressure on the freezing point of liquid.
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EQUILIBRIUM I 7141
-
CARRYING 5 or more MARKS
srt.7.1. What do you understand by 'Equilibrium' ? Discuss one example of each of lhe followiDg physicnt
lo 7.3. equilibria:
(i)
(r)) Liquid-gas equilibrium
(iii) Solid-solutioo equilibrium
(rv) Gas-solu tion equilibrium
Give one importaot characteristic ofeach of the above equilibria.
Scc. 7.{. ,- Briefly explain the foll@ing :-
(i) Reversiblc and Irreversible reaction
(ii) Dynamic nature ot chemical equilibriuDr
3. Briefly explaio the important characteristics of chemical equilibrium.
S('c.7.5. 4, State and explain the Law of Mass Action. Derive the Law of chemicalequtllbflum and heoce define
1o1.6. equilibrium constant.
Scc.7.7. What are lq atrd ? Derirc a relationship bem,ern them.
\
Sec.7.E. 6. Erplain the effe€{ of the following on the equilibrium constant.
to 7.9. (i) Concenhations of the reactaots are doubled
(ii) The reaction ls reversed
(rir) Catatyst is added to the re€ction
(rv) Tbmperature is iocreas€d. R
7.
EE
Scc.7.l0, What are Horrogencous and Hetetogeneous equilibria ? Give three eEmples ofeach. rr\'trite expres-
lo 7.12. sions for their equilibrium constant and give its units in each cas€.
AR
8.
C
Sec.7,l1 State and explain Le-Chatelier's principle. Discuss its application to the manufacture of
to 7.15. (i) NH3 by Haber's process
S
N
t
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<_------r
No. of n]oles before dissociation I 0 0
IIT
D+-D
7=-r= t +,t ot a=7- |
C+afV
D-d
o=--T- ...(ii )
7142
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EOUILIBRIUM
- I 7143
Al ternatively, observed molec,ular mass can be calculated from the mass of a definite volume ofthe vapour
at a particular temperature, using the relation
pv-#Rr or M"=iS ("", =#)
In case ofdissocistion ofN2Oa , we can write
N2O1(t) \-r 2NOz e)
No. of moles bcfore dissociation 1 0
No. ofmoles after dissociation l-.I 2a, Tota!=l+ d
Henc€ the same formulae will apply as for the dissociation of pCIs .
"'
;";.;;;;;,,:,',,,,;;r
S
N
IA
1. f! 3 celai! tempcrature, the vapour densiry of 2. I 588 g of N2O. givEs a total prdsure of 760 mm
.
Q. 2. Show that the degre. ofdissociatior (a) for the Neglectingr in comparison lo unity
dissociation of PCls into PCl3 atrd Cl2 ot pres'
- or ,= /lq )'"
C
Kp = +Jp
S
[oE
N
surepis giyen by l ,J
_-
rt=
ppor, po, (#,')(#"i ;P Q 5 Whst is the effectofreducinB thevolurDe on the
= p"o, l-a' srstem described below ?
2c(s)+ o2E) + 2CO(8)
or 1r -a215=azY (B.I.T Roachi 1990)
co& yst (ii) hcccsiDg prrssnE ? l(t - a)t 2(z - a)lp x teTt -;f / Be --.yl
N
IA
AIrs. (i) No, because cahlysi does noi disturb the state
_ t6 a212 - a)2 |
of equilibrium. (r'i) No, bcc€use z, = nI
l(t -;I-P
IIT
Fi)r the reverse reaction, 2 AB <::.A2 + 82, concentmtion of CO to 0 6 mole by odding CO2 into the
equitibriuD constant = 1 ./ Kp vessel how maoy moles ofit must lre added into eqoi_
librium mixt[re ot conshnt temPernture in order to 8et
( )n drvr(trng b) 2. AB + ) nr - lur, this clrange.
Slrlution. Step l. 7o cakulate Kcofthe rc.Etion.
equrtihriurn (, rnsla,'ll I r'K;
.. ICO G)l lU2 (8)l 0.2 x 0 6
K. = =0 xrl 3-'
lco, Gtl luF€)l 4
Ammonium carbamate decomPoses as
NII2COO NII4 (s) + 2 NH3 G) + co2 G) Step 2.To colctthle efrra Cozlo be ad.led
ln,r (losed vessel containing ammonium car- Suppose extra COz to be added = -r nlole Then
hnmxte in eqrtilibri[m, Nll, is added such that the writiDg the reverse reaction, we have
partinl pressure ofNIIS now eqrlals originarl tot[l pres_ COz + II2+CO + H2o
sure. Calculate the ratio of tohl pressure now to the 06 04 03
Initial nroles O2+x
originxl pressure.
after addition
Solution. Suppose the totalpre$sure ofthe mixture
lDuially is P This is due to NH3 and Co2which are Present
2+r-0 2) (0 5-0 2) 0 6 (0 3+0 2)
Moles (Molar (0
conc.)atnew =x =0 4 (Given) =0.5
rn rhc ralto o[2: l. Thus7"r., = i t ,ao, = ] O
equrlibriunr (V = lL)
1 0 ('x0 5
K. =it= Iorr=0 75mole
- K, = (PxH,)2 (Pco,,' = (?r)' (lr) = +r*
Alter adding NH3,pps, = P (Given) I t,)J,!, n 1
Thedegree ofdissociotior ofN2oa into
- a-L
R
NO2 ot ore ntmosPheric pressure nnd 313 K is 0 310.
EE
Pz x pcot=Ko= *P' ot Pco2=frP Cslculate Kp of the dissoclotion rerction nt this
AR
' Total Pressure no\{ =PNHI + Pco2 temperature, Whot rvill be the degrec ofdissociation at
10 atmospheric pressure At the sahe temPerature ?
C
=P ' ' -- 3l o
+rlt Solution. For the dissociation reaction
S
27,
t' 2 No2 G)
N
N2Oa G)
'. t{atio of total pressure now to the oriSlnal pres-
IA
3l molcs I
lnilial 0
=,
IIT
SUfe
Molesateqm. 1-0310 2x0 310
The equilibrium const[nt ofa reaction
(z=0 310,Given)
doubles on increosing the temperAture of the reaction
from 25"C to 35oC. Calcrtlnte enthslPy change of the =0 69 =0 62
rou z :
,^.., a H' (308 - 2e8) K N2O4 2 NO2
-,r8T 3o8T-
=
,Jo3;lil; rK:r;;F ' Initialmoles ----------r
01
or A H' = 52898 J nrot-1 =52 llgt kJ mol-l Moles at eqm. 1-a , 2d, Tbtal =1+d
Prubleh An equilibrium
mixture
x to atm
CO (g) + H2O (g) {r CO2 (g) + H2 (8) Present in nnroo= # 'lo atm' PNo2 = ?f;
:r vessel o[ one litre caPacity ot 1000 K wss found to ,, [20 at 1l + a1]2 4o az 4O az
contain 0 4 mole olCO,0 3 mole ofHrO,0 2 mole of tr? =
ili[=rd=;]=1r= dIT -
+a--7
CO2 .rnd 0 6 mole ofH2' Ifit is desircd to iDcrease the
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EQUILIBRIUM I
- ? 147
.. 4o
l-r,'"z- =o
tzs Zr.lH., x =\pHrs
p x (p + 0.5) = 0 11
NcglcctNe a2 in comparison to 1, 40 a2 = 0.42.5
or p2 + O S p = O 1I
or a=0103=lO37.
or
'' ,,/,, rr . Wlren d - D glucose is dissolved io /r2+ 0 -5p - 0.1I = 0
water, it undcrgocs m[tsrototioh to form tln equi- y'@.sf
libriuh mixture of a - D glrcose and p - D glucose -o s= -+t-n.rrl
conlflining 63.6qa of the latter. Colcrlflte K. for the
mutnrotation. - os t Vo.Zi=i:At
2
S!I]!iq!."- D Blucose s__ P - D glucGe
! Vo;g
At equilibrum 3(,.4Ec 63.6%
_ _ 0.5
2
r"=ffi= r tat = -0
5 !0 83
=
0 33
o trs
!" t,/.lt /,
--=
At77.Cand one atmospheric pressnre, . -i-
PHrs = 0 165 atm, pps. =0 665 atrn
NrO. is 707o dissociated into NO2. WlrBt will be the
volumc occupied by the rllixtrrr uDder thescconditions (Ncglectiug _vc valuo)
ifwe st{rt with l0 g ofNrO. ? / One mole of lI2 and three rnoles of lll
Sohttion. Molar mass ofN204 are injectad in a litrc flask Wtotwill be thc concentrr_
tion of H2,I2 flDd tll at eqrrili}ritlm at 490oC ? Tlrc
= 28 + ()4 = 92 8 not-1 equilibrium constrnt for tltc reaction at 490" C is 4S.9.
NzOl <------\ 2 No2 (M.L.N.R. Allalnhad 1 99 5 )
Initial moles *g
Sol[tion. IIu
R 12 + 2ljl +
EE
9) 0
Initialconc. 1 23
AR
K = :J+lr)'?
(t -x)(2-x) - e+4L+ l2.r- .lse
IIT
statc. Calculate the Percentage of iodine conveiled hto solutioD. +N2O4 G) 2 NO2 G)
III (K. ot 40-C is 0 02). (Bihat 1997) InitialamouDts 0lnrole 0
H2@) + tz (8) <-.------\ zHr G) At equilibrium (0.1 -r) 2x,
lnrtial 2 3 0 moles Tbtal=o l +rmoles
At eqm. 2-x 3-x 2x As P=latm,
2x 01-r b
Molar corcs + + v Pxroo = oiiai, PNor=tl-l +r-:atm'
-. (2t / v)2 pfr",
r{c=iE=t7vJf(3--_r-DlVJ v.? - ------1
pnroo
'-2
= lz-x)lr
---*.-----= = o 02 (Given)
-x) x\z 4]
This oo solvi[8 Sives-r = 0 1615
=ffiot/ 0.1 +
=?0-:1=lt?d +rt
. 7o of iodine converted into HI
'
4?
-o 3 1615xloo=53E7a 0.01 -,r
t\ thtt n ltt 0. 1 mole ol N2O. (g) was scaled in a
4P =0.14 or 4.14f =o.ool4
=
0.01-r2
tuhe under atmospheric conditions {t 25oC. Calculate or x=0018
the number of moles of NO2 (8) presetrt ll the cqui'
.,
INS ) R
SI?EC'AL
EE
AR
C
4?t2xl2
IIT
.Thcse bcing originat prcblcms e5 askcd in thc compciitive examinations, ai many places units of \ and Iq havc bccn
coDcs at eqn,I.
tABl2
K = tArl
S
tBrl
N
D
., A=r+Zot
IA
a
or so =
r;qr=r
IIT
(r-l
t-3- J
On soking, we get x = 0 . 955 mole
Hence no. of mol€s of AB formcd at eqm.
r)
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7150
. K,=-;6;=-7:;1= 1z I
#-
S
m 4f +2 2P =o 6048 - 4 32P
N
0 3025 +
IA
,{s Kp for this reaction isvery small,, < < l.Thking 4p2 + 6 52p - 0 3023 = 0
IIT
.
l'=----2,,
Moles of H2 present-l 6tl = 0 4S8
at eqm. =0 rltole
ApplyiDg PV = ,RI
Total pressure at eqm. = 2 atm (Given) x2.5 = 0.458 x 0.0821 x 750
P
Total moles at eqnl. = 4 or P = ll.Ztotm
z.o=#x2=l 16etm I'n,hl|'n I I A ye-lisel at l0O0 K contains c{rboll
dioxide with a pressure of0.5 atm. Some ofthe csrbon
I- 0.681 dioxide is converted to carbon moDoxide oD addition of
PH2o = ----4- xZ=016atEr graphite. Calculote the value of K if the to&rl pressure
0.681 st equilibrium is 0 t ath, (Iloorkee 199j)
Pcor= PlH, = --Z--' Z = o J4atm.
Solutiop. The reactioD is
I'rohltnt 10. 0 15 mole of COtikenin2.5Illask R CO2 E) + c (r) 2Co (s)
-=+
EE
is mairtAincd {rt 750 K llongwith a catalvst so ihat the
following rel|ctioD can Llrke place. Suppose decrease iD pressure of COz after reaction
AR
co G) + =p atn'l
2H2 G) <- crr3oH G)
Then increase in pressure due tb CO 2p
C
(i) I<}and Kcarld (ii) thelinal pressure ifthc sEme ''' p = 0.3 atm. He nce we have
IIT
nDourt of C0 and [I2 ns before are llsed but with rlo PCO\=0 5 -0 = 0 2 atn]
3
c{tslyst so that the rciction does not take place. and pco=Zxo.3=06atnl
(I.I.T 199j)
Sohtion. (i) CO + i-
rio
D7
ro er2
2Hz cH3oH
pco2 =E:=tt
lnitially : 0.15 Drolc
At eqm. : 0. 15-0.08 mole 0 08 ntole
= 0 017 mole
Totalvoluore, Y = 2.5 L, 1000 K. For the re.lctioD
'Ibtalpressurc P=8 5arm, T=750K. 2H2S G) + 2H2 G) + sG)
Applying PV = ,RT the value of K. is I 0x l0-5 (Roorkee 1994)
we get 8.5 x2.5= n x0.0821 x750
or Soluton. Molar conc. of H2S a-,
a = 0,345 mole -- ffi rno,
. No. ofmoles ofH2 at equilibriunt
= 0 25 mol L-l
= 0 34.5 - (0.017 + 0.08) = 0.248 mol Suppose degree ofdissociation ot H2S
,. = a. Then
rc" = 0 017 x8 5 atm o
o.ET = 42arnl
HzS (----...: 2H+ + 52-
^.p: - 0.248
O-as x8 5atm=6 llalm Iniialc!nc. 0.25 M
-rcH3oH = 008 Conc. at eqru.0.25 (1 - a) 2x0?5a 0.25a
n.3?5x8 5atm = I 97arm
= 0 5a
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llralaalr's Neur Coursc Che m i strgLJifrlll
7152
H2 + Br2 <- 2HBr
Iq= lnitial 0 6nlolc 02mole
(O .s a)210 25 a;
amouDll
.^-6
Ir, - = --ll)5-[l-;,
0'25 a2
-1 _" r) r) 2x
Amourts (0 6 - (0 2 -
Neglecting a in conparison to 1, we get at eqn]. moles
rcactioD is imPossible.
aorount ofAg
= 1.2moles
If V
11# = o zu
S
0.781 - 0.219
llence derisity (D) * +
IIT
D-d t -r, 2.
'd Prroa = iTi r Pdr)d pNo2 =ff ^ P
PuttiDg Kp = 640 nlm (Given) afnl equilibrium the solid decornposes into goseous nmmonia and
hydroEen
' 6nlPhide.
pressurc, P = 160mDl,weget 6ao:4x$o lil C.t.rtot. X. aDd Kp for the rcoction ot 27oC'
(ii) WhEt ttrottld hopPen to the equilil,riurr *hen
1 more solid NHaHS is introduced into the flnsk ?
o' Lr-o'=1 o' o2=l-J
(I.I.T 1999)
or 2,] - 1or"2 =O 5ota =o 1o'l =7[ 1qo (i) NHaHs (r) + NH3 (s)+H2s G)
For dissocatioo to be 5O%,a - o 50,Kp:640mn] IDitial 3 06 g
rconsranr) +t0,5'12. amouni =3 06/51mcle
- I (r 5r ^ e
ooo
= 0 06 Dole
- 1n
rJ At.eqDr.006-iffix006 0.018 0.018
rrr tr40=-r-TP=iP or P=4lt0mm
r-i =0 06-0 018
mole mole
400 K anrl 1 0 atm for the gsseorts reaction PCl5 t' Eq0r conc.s. 1 0.0182 0.0182
92
14 upon the alnount ofNH4IIS (r). HeDce thcrc will bc no
S
- contniner is 0 t atm at
Tte total pressure of lhe
Kp = K. (RT)^" = 0 04 (0 0821 x 540)1 = 1 77 Z0'C Defore the reaction' Dctermine thc final pressrtre
'
When 3 06 g ofsolid NIIaHS is irtro- at 120oC after rcaction assuming t07o yield ofwoter'
duced into a twoJitre evacuated flask at 27"C' 307o of
(Roortue 1999)
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EOUILIBRIUI\,4 7155
- I
2NO + 2 Nocl
(d)cox@) + c G) + 2coG)
Initial
C
0 02 atnt P Atm
Suppose at equilibrium, pressure of
*"c,.(ooz-ffi) (,
S
q#
H
N
CO (t co) = p atm
IA
l0-l =
- 10 r y'T00-=?=Zo-0-f
=---,--=3.66atm (t98x1O-')2x(r-10-1
,4.
Thus ai eqm.,pco = 3 66 atm, or(P- lo ')=fiqlzx113=o 1
toz
Pco2= 5 -3 66 = 1 34atm or p=0102+00001 =01021 arrn
Applyrng PV = r, RT Volume ofthe vessel can be calculated as folloPs:
l. Reactioo between iron and steam is reversible if il 7, According to l-c Chatelicr's principle adding heat
is carried oul to a solid and liquid in cquilibriun'r will cause the
(d) at constaDt temperature ,{€) amount ofsolid to decrease
(r) at constant pressure (6) anlount ofliquid to decreasc
(c) iD an open vessel (c) lemperature lo rise
(d) in a closcd vesscl. (d) temperature to fall.
2, The relatiooship bet*een Kp and Kc is iJl.l"N'R AlllJnbatl Ie90 )
t. In a reactioD 426) +4 BzQl)+ 2AB1g),
(aiK" = K,(Rr)^" 1tyt<.= 5lnrl-& AH < 0. The formatioo of AB4 G) will he fhvoured
= x. (nr)-&
,tdx, (.1) None or lhesc is correct' by
3, The equilibrium constant for the rcaction (4) lov le$perature aDd hiSh pres\urc
N2 + 3H2 <- 2NH3 is K. The equilibrium (6) high temperature aDd lo\x pressure
constant for (c) low temperature and low pressure
(d) hiSh temperaturc and hiSh Pressure.
lvrrlw, ;4 vH, w1169
R (1.1.'I 1990)
EE
(o)K / 2 (b)2K 9. The reaclion which proceeds in the forward direc-
pflK
AR
(d) K2 tion is
4 lf an inert gas is added to the equilibnum mixture (o) Fe3Oa + 6 HCI = 2 Fecll + 3 I-I2O
C
of the dissociation of PCls iD a closed vc'sel, (b) NH3 + Il2O + NaCl = NHacl + NaOH
S
N
(a) the concentration of Cl2 will incrcasc (c) Sncll + H82Cl2 = SnCl2 + 2 HSCI2
IA
= 2 Cu2+ + 4KI.
(c) thc coocentration of PClj will increase tl L'l: 1let )
(d) the cquilibriunr concaDtralions will remain un' 10. For which of the following reactioo, Kp = Kc ?
affecl ed.
(4) 2 NoL-l G) # z t'lo 1r1 + ct2g\
If pressurc iDcreased on the equilibrium
is
Nz + oz <=+ 2 NO, the equilibrium will <=--r 2 Ntl3 (c)
(b) N2 G) + 3 I12 G)
(a) shitt in the forward directioo (c) H2 G) + ch G) s- zHCl (8)
(r) shift in the backward directioD (d) 2 Nro4 €) <: 2 No2 Ui)
t
(c) renrain undisturbed
,1.1. L l99l)
(rJ) may shift in the lorward or backward drrectioD ,. ()z
. 11. ln u vesscl ,jnnlainlng S()3 . SOz and irl cQui-
For the reactioo
PCl3 E) + cl2 (S) PCls Cl)
'' librium somc heliuol sas is introduced so that lhc
+ total pressure increases while len'lperature and
the value of K. at 250"C is 26. 'lhe value of Kp at volunle remaiD coDstant Accordlng to Le
Chatelier's Prlnciple. Lhe dissociatroD oi S()3
this tcmperature \4ill bo
(?t) 0.61 (a) increases ,,@j c""r"^o
,lu1o-s'l
(c) 0 83 (d) 0 46. q;)remains unaltered bly.
(M. L.N. R- Allahabdd I 990 )
\ ( I'
iis
l. .l 2,b 3.c 4.d i.c 6.a 7. t E.d 9.d 10. c
ll. ,
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EQUILIBRIUM 7157
- I
12. lD a rcversible reacti()D: t\+'o substances are in equi- 17. ln 2lII Hz + Iz, thc ti)rward rcitction rs
librium. Ifthe concenlration ofcach oDe isdoubled. r,lccled =-
by change in
lhe equilibrium constant will be
(4) Catab6t (1,
) I'ressure
(d) Rcduc]ed to half its original value
(c) Volume (d)'lijnrperatoro
(D) Ilcduccd to onc lburlh of its original value
(c) Doutled (d) Coostant.
lll\Ofttut L"L.L l. It)ttJ
l& 64I of HI arc prcsent in a 2litre vcssel. '[}!c adivc
t,lI.L.N.Il. rlllalubad I9t)).lt.l.7: lt .hi l,t))) mass o[ I{I is
Ir. AD equilibrium mixture for lhe reactioD 5
(a) 0 <bTO.2s
2 HzS (B) s-:-: 2H2G) + sze)
.(t)l0 (d) Noneol the rhrce.
had I mole of HzS, 0.2 mole of H2 and 0 8 mole t Ih1^a,u (.1).L.1: lee:
of 52 io a 2 lilrc flask. Thc value of K" in mol L-l lt . The equilibnum consrant (Kp) for the roaction
ts POs G) + Pcl3 G) + cl2 g)
is 16. It lhc
(a) 0.fi)4 (r) 0.08 lolume of the oontainer is reducrd ro one-half of
(c)0 (l 16 (d)o.l(ff. ir r.T 1ee2) ils originalvolumo, the value ofKp for the reacrion
t*-ln what maDner will iDcrease ofpressure affect the at the same tempeEturc will be
" lbllo$'ing cquilibrrunl 'f Q1'tz .
(D) 64
C (r) + Il2O G) <=:+ CO E) + Hzo (f )
r<c) t6 ig)+.
(a) Shili in the forward direction l)t
-/..-t
(r) Shift iD the reverse direction ,4zlnarw;aion,A + of
(c) Increase in the yield of hydrogen A 3.0 mole of 'B'a in
(J7lio (LLT. 1991i
R a 2.0 L flask and the e4uilibrium concsntration of
EE
en-ect.
'C'is 0.5 rflolc/L The equilibrium corshnt (K) for
15. 'I}le rcaction, SO2 + Cl2 i- SO2 Cl2 is ex.
AR
SO2 E) , cl2 E)
and SO2 Cl2 G) is atequilibrium in (d) o.026.
S
truc ?
co[taiDcr uDdcr one aunGphere. It is heated to
({n K s,hen 2070 by mass of N2O. (g) decompces
(a)The pressurc inside the container will llot
lo NO2 (t). The resultant pre.ssure is
change
(D) Thc lemperature will not change (a) 1 .2 (b)2 4 a.m
"tm
(c) The temperature will iDcrease (c) 2 0 atm (d) t.0 atm. I.I.T tss(
(d) The temperature willdccrease. 22. If the colc€Dtratioo ofthe reactaDis is lncreascd by
r, theo equilibrium constanl K becomes
I S ll l)tutlhLt.l. it)t):
16, The equilibrium coDstant for the reacrion, ... K
trtln- (r)+
x
N2G) + ozG) <- 2NO(a)is4 x l0-1ar
(c)K+r ldJx
2ffn K.
In prescnce ofa catalyst. equilibrium is attaiDed ten
A.Etl.C. I\tw 1997
23. In which case Kp is lqas than Kc ?
trmes faster. Tberefore, the equilibrium constant,
in presence of the catalyst, at 2000 K is: (rl)PCl5 + PCl3 + Cl2 .
165 t x ro-a
(a) 4O x lO-a (b) H2 + Cl2 + 2HCl
(c) 4 x 10-3 (.) 02 r=l
2SO2 + 2SO3
(d) difiicult to compute without more data. (d) All ofrhese it.E]I.C. I'tru 199i
IM.L.N.R. Alhtuhtd, 1994 t
A]VSLL'FRS
12. d 13. c 14. b 15. c 16, b 17. d llt. , t9. c 2lt. t 2t. b
22. d 2i.
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758 N e.4
24. If Kl and Iq are the respective equilibrium con- 29. For the chemical reaction
staDts for the two reactions 3 XG) + Y(g) + X3Y (8), thc amouni of
affected tY
XeF6 G)+H2O 0I) + XeOFIG)+2HFG) X3Y at equilibrium is
(c) conc-1
-4'1 s)
,!81More of thc product will be tbrnled
(c) More of lhe reaotants will bo formed
(d) It remains unaffected. rl).c.l: Ii li. 1999)
Forn]atioD of SO3 takes plac€ acaordiDg to the
32. For the reaction !I2 G) + 12 [C) + 2 Hl (8),
reaction
2SO2+ Oz 2SO3, arl = -45 2 kcal
R
the equilibrium coDstaot Kp challges with
+
EE
(6) temperaturc (b) total pressure
Which of the following factors favoum the forma-
AR
(D.C.D.E,E. t999)
(a) Increase in temPerature
S
,I
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EOUILIBRIUI\4 I 7lsg
PMso x Pco. 41. WheD two reactaDts A aod B are mixed to givc
(.) It = /r,rscq @) \ = pcoz. producls C and D, tbe reactioD quotie[t, Q, at lbe
initial shges ofrhe reactior
lc. lr.s. li. l!,t|.'l: )0t)t)) (4) is zero (lr) dccreases wil.h timc
36. What happens to the yield of this reaction whcn (c) is independent ot tin]e
tcmp€rature is incrcascd I (y') iocreases with tiorc. (1.1.7: 2ooo)
Nz+()2 # ZNO;+:.Zt<cat 42. At corlstant len]perature, the equilibrium coDstaDl
(4) increases (D) decreases (Kp) for thc deconrposrtion reaction
(c) remains samc (d) NoDe ofthese. N2O1 <- 2NOz Ls expressed by
\ 1 11 i - trl Ke= Ot \/( -l; where P = prcssure, r =
,, 500 mlvessel contaiDs I 5 M each of A. B, C and extent of dccomposition. Which one of tbe follow-
D at equilibrium. If 0.5 M each of C and D are ing statemeDts is true ?
. rakcD out. lhe \alue of K. lbr A+B # f;+O (.r) Kp incrcascs with iocreas€ of P
will be
(6) Kp iocreases with increase ofr
kr1 0 (b) lB
(c) Kp increases with decrease of.r
(c) 4/) (d) 8B
(D.('.1,.E.L: )0(1(1t -€+Kp renrains constant with change in P andr.
3ll" Al 25'C the value of Kc for thc reaction . (! l.T 2t)01)
jI
x, + o, <-----r No2 is 2 x lty'. whar will he
23. 5 moles of SO2 irnd 5 moles of 02 arc allowed to
.l
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7160 Netd Course
46. lf N2 + 3 H2 s---------r
2NH3-K then lNH.t2
is siven rry e=
2N?+6t12 4 NH3-X. ? INJE;p
=- 'lte reactioD
6x, (D) r'Ir (c)t/,/K glrt* (a)Q= K.
will proceed from riShl to left
0,)o.q (9Io > \ 1l)o=tt
if
(Roids nn llll.T 2t102)
47. In thecase ofa gaseous homogeneous reactioD, thc
i(.ll.s lt. Plt l: )0t)iI
active mass of the reactant is obtain€d by the cx- 53. The following equilibria are given
Prcsslon
N2 + 3 FI2 <:l 2 NH3, Kr
- PV (a)RT
(.,)nT -,.P c)+ r\9o N2 +
H2+ioz <-
I
Oz i=:= 2 NO,
H2o, K3
Iq
\'tanil ,\'du L.l .'l: )olt)
4tl. In which ofthe folloBiDg equilibrium, change in the Thc equilibrium constant of the reaflion
volume ofthe system does Dot alter the nuDber of 2NH3+iO2 2NO+3ll2o
moles ?
+
in terms of Kt, Iq and Iq is
(d) N2 G) + 02 CI) i-s 2 No G)
(r) g) I! Iq
(a) Kr (6) Kr rqlrq
PCr5 E) <-PCt3 G) + ct2
(c) N2 G) + 3 H2 G) u-------s
2 NH3 G) G)\Rl/tq .\dIK2Y'.tr/ Kl
t(.8.\ li I!.11.7: )oo l
(d) so2cl2 (s) + so2 G) + cr2 G)
For the sfnthesis of ammonia by lhe reaction
trll l: l. :t)tl) "64.
' Nz +.1 H2 + 2 NH3 in lhe Haber's process,
49. I moleofN2 and 2molesofl{z are allowed to react
the attainment ofequilibrium is corrcctly predicted
ia a 1 dn| yessel.
At cquilibrium, 0 8 molc of R hy the curve
EE
NH3 is formed. The concentration of H? in the
z z
AR
vessel is o I
Gr)O 6mole (r)0 8mole =
2i
C
, '
=6z
zo
IA
)
(c) r'ET- (d) r.o
N
,r( _s
(t5. a
56. c 57. c 5t. a 61, c 62. c 63. e
66. c
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7162 Netl Course Che ruisttg
l. As othcrwrsL thc I{2 gas $ill cscirpe Applying PV = zKI] 1 x V - 1xRx3fi) ''(i)
2. Kr = Kc (RT)^' or Kc = K/ (RT)- ^n f
Whcn z = 1.2 mols, = 600 K,
PxV-l2xRx600 . (t/)
4. lu a closed vesscl, cor)ccntratloo$ of reactanls and
Dividing 0i) by (i), P = 2.,1 atnr.
products do nol chrDge ort addins in€rt gEs.
6. (RT)A" = 26x(0 0821xs23)-l = 0 61'
22. Equilibrium constant is constallt at constal,lt
Kp = Kc
temPerature-
7. S()lrJ + l{eut # l-iquid. Adding heat wrll
shrll lhc cquilihriirm in lhc forward direclion. Kp - Kc (Rf )e. Kp is less thon l(" if aa = - uc i.e.
!t. 'l'hc given reirctioD is exotherffic (all < 0) and
lccomp nied try dccreas€ ir thc trun]ber of moles
IIcncc it will b,e fa\oured by low temperature and ,.
trr =
fxeoFollHFl'? ,, lxcot'al lxco3l zl
|\' =
high pressure JF4ITrJFI- lre-oJTxE4I-
9. FcCl3 alld I IzO do nol react to Eivc bsck FcaO4 and .. [XeO3F2]
Atm: -
Illrol Ka
HO. lxeo;l IHFIr Ri
11. Sec IliDt to Q.4.
12. Equilibrium constant ofa reactioo docs not depend
upon c([lrfcnlrations. [t is cotlrtant at cooslallt
x.=ffir=ffi'"'n"'
IH"ol6
tNol1 .^----.ro
t cll't pe ra Lu rc.
But with respect to stirndard stale concentration ol
14. ll)c for$'ard reaction is accompanied by the in-
crease in (he Dumber of gaseous moles. Hence 1 mol L-1, it is dimensionlc,ss.
R_
r- /_ l\
EE
incrcase of pressure will fflvour the reverse reac-
tion.
&,s= I\I
*Z) =-Zt
AR
t5. SO2 + Cl2 .- S(]161, + Ileat. OD adding xrz f. = 1nr;& = (RT)- 1/2
= t r r4{T'
C
SO2, thc cqurlihriurn will shitl fon ard is. nlor€ Back$ard reaction is dissociation reaction and
S
heat will be c1,olved. So tenrPerature will Increase, henct endothennic. The forward reactioD will.
N
16.
cousfant tenlpcralure. paoied try decre&ie in the number of Saseous
IIT
17. Ir is an endothcrmic reaction. Hence equilibrium is moles. Hence its equilibrium will b€ affected try
tempErature and pressure.
affgcted by tcnrperature,
I{l = On addilU iDert 883 at coflsmnt prEssure, di$socia-
1E. Mol. mass of 130,
tion i[creases i.e, more of tho Produus will he
. Ilrrl =ffi"1=o zs. formed.
Equilibriunr coostant changes only with lcmpera-
19, Ki, docs not depeld upon voluD'lc or coDccDtra-
ture-
li(n)s. It is cor]slatlt ilt coosunt temperatute
3s. [Solidl =
20.u\*28+2C 1.
1.5 Y 1.(
lDitillconcs. 1molL-l 5motL-l 1 Imoll--l fl. X" = i# = l. ()n char)grng uoncenl rll iot1s.
=l ls =:0 nrol I-l 3& The reactiol is rel,ersed alld nrulliplie(i try 2, thcro'
mol t.-l nrol L-l [or( equrlrhriun] conslr,tt -I K?
,, tu 5t2 = 1 ,, 12 x ltlalz =
'
N= 0't)5 -'1-
a toT
l15 \ edr = lo. X. = X, z1n'r1&
^
21. NrOl (- 2 NO2
I
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EQUILIBRIUM I
- 7163
HIN:T6 CONTD.
42. Kp is corsrant at constanl temperature.
Aim:K- lNolr llr,olr
''' K, Kj
4.3. 2SOz + Oz <===+ 2SO3 = _j-
Kr
lNHr12 Jo2]5/2
Irrtial molqs 5 5 54, (a) is ccrrect hecnuse coDcenlrations ol H2 il,td
nr cqnr. 5-TfrY5 5-1.5
r,0
1 N2 decreaso wi$l time while that o[ NII3 incrclses
wilh time ancinfter equilibriunt, irll olthem remiliD
=s-3=2 =3.5 constant_
'lbral=2+3-5 +3 =8 5
44. l(15 <_=+ PCll + Oz
5s. r\. =
lPClrllclrl
Molcs xt eqnt. 0 1 molc 0 2otole 0 2mole JpfXT_
Mohr coDcs. 0 1/10 O A:(t 0.2110 0.2 x lCl- l
r." o 5= rrr l( lzl - I (t nr,'r l r.
ntol dar-l --57-4
tr. Ice <=.J Whrcr.
x=!l${f14=o 61 Morevql. [,e$s vol-
45. lnitirl IN2Oa] =9 2/92moll,-l On apptying prss.\ure, equilibrium shifrs k) the si(lc
in *hrch volume is les.
=0.1nrolL-l 57- l'he givel rerclioll is endothcrn]ic.9l on increJs-
At. cqn]. (aftcr 50% drssociation),
rng temperaturc. it will shilt in the forward dirccti(nr
IN2O4] = 0 05 M, [NOzl = 0, I M 5ll.,trr=1-2=-1
I2
,, I't(,21
'r1,1 r0.1lr K.(t(f)-r=
K =
iNJIJ ='Ori- =u I R Kp = I(" (R-l')^, = K..,lLI'
EE
,17. 1\cllvc l'lilss = Molar conc =
or Kp,/K. - 1/RT
AR
4t. (lhangc in voluDe changes the molar coDccDtra- 34gNfI, = 3,f ,' tl = I
N
n1;1g\
IA
IH.OI slot ,
,-#i:i#';
is used).
' lurl lo,l''' 61. Suptrce NO2 -.rg- Theo NrOo = (lur _.y).s
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7164
Pr^lear's Net4 Course Chem istyqllft[)
R
ADD'T'ONAL uEsrloMs
EE
AR
Exarninati
C
Ae s erAi on -Re a s on T,
V V e Q.u e sAi o n s
S
N
The folloyilg questions consist oftwo st{tcmenLs, pritried as acseltion nnd Reasoh.
q{estions, you ort required to choose tlny one ofthe tollowibg follr responscs'
IIT
(a) Ifhoih A.ssertion and Reason are true nnd the Reason is the corrcct explanation of thc asscrtion.
(,)IfhothAlrserlionondReosonartttuebutreasonisnotacorEctexphDlrtioDofthe,Assertion,'
(c) If Asscrtion is true hrlt Reason is false.
(d) IfAssertion is tolse but Reason is trre'
(?) lf hoth Asscrtion ond Reoson sre fglse.
Assertion ReflsoD
The equrlibriuD coiffiifE fixerl and charac- The composition of the-firnlequilitrrium nlD(ture
ill a
teristic for any Siven chemica! reactlon at a paflicular temperaturc depeDds upoll thc starting
sp€cified temPerature- amount of reactants.
whe n a calarysl is added to a reaction mixturc in
'Ihe forward reaction becomes faster on adding the
equilibriunl, the amount of the products in' catalysl.
cteases.
Adding i[ert to dissociation equilibrium of Molar coDceDirations
SiLs
of the reac(anl5 ilDd Products
NrOn at consmnt Pressure itnd tenlpcralurc in- decrcasa-
creasqs the dissociatiotl.
4, Kp is lways Sreater than K". Ite efTcct of pressuro is greater oll thc ralc of reacliol'l
than the cffect of conce[tration.
5, Equilibrium constant of a reaction lncreases if l}Ic forward reaction bccomes taster with lncrease ol
temperature is increased. teD'rperature.
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EQUILIBRIUM
- I
True/False 9tatemente
Whlch ofthe follorving statements flre false ? 4. The equilibrium constant of a reaction is in.lc-
Whe[ equillbriunl is attaiDed, tbe conceDtratioD of pendcnt of the concentratioDs oftbo reaclants.
e{ch of the reactants and products b€comes equal. 5. There is no effect on the equilibriunl conslaDt of
BurniDg of magoe$ium to forn] MgO tS an irre- H2+12
-=l2HI. if some inert gas is added to it.
versiblc process. 6.'fhere is Do effect of pressure on the dissociation or'
EquilibriuD is disrurbed ifcatatlst is added m it. Nzol'
R
EE
AR
C
S
N
IA
IIT
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L' hg OT
Equil,bri ur rn-l I
(tontc EquiltI)num tn Dotuuons,
Equilibria involving ions, various concepts o, acids and basee-Arrehenius, Btonsted-Lowry and
Lewis, dissociation of acids and bases, acid-base equilibria, ionization ol water, pH icale,
hydrolysis of salts, PH cElculation of salt solutlons, acid-base tilralion using indicator, solubility
equilibria-solubiity ot sparingly soluble salts, solubility equilibrium and solubility produci,
comrnon ion effect, elernenlary idea of bufler solulions.
1;;;;ffi
R
,4 strong electrolyte is defined as a sub*ancd,
EE
..l,7 ffioll4o E tufrtrd B a wryoud vlw ,4 wcak electrollte ir delined us a sub$anre which
N
811
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812 Net4 Course Chemi str4
cH3c(x)H + I{2o <----\ cH3coo- + H3o+ inversvl! proportional to lhe square rool of molor
C
Apptying law of chcmical cquilibrium, concent ation or directl! ptoporlionul ao lhe square
S
lCH3CooHl x lHrol
IIT
REMEMBER
In dilute solution, [HrOl is constant. Thc
product o[ K and constant [HrO] is denoted as K,, (i) The approximation 1 - q : lcanbeapplied
tlte ionization constant or dissocidtiott constant of only ifa < 5oZ. lf on solving a problem by apply'
tha acid. Thls ing the approximate formula, a comes out to be
COO-I x
lHsO+l > 5'%, lhe problem may be solved again by
K" = ICH1 IctrpooHl "'ir) upplying exact formula irnd a may be calculatcd
by appllng solution of a quadratic equation i c
ll 'C'represents the initial concentration o[
thc acid in moles L-1 anda, the degree ofdissociu- -u *,/F
2a
-tri
tion, then equilibrium concentration of the ions
(CH3COO- anil HrO+) is equal to C(I and that o[ (ii) Ostwald's dilution law is applicable only to
tho undissociated acetic acid = C (l - a) i.c. we weak electrolytes because for strong electrol}{es,
havc .! = li.e- Ka + @.
p,R.o.,. b,
EF_ M.8., 9i .11 .,,
1', 1,,), 1]1i.,u :l
*]:u,1
lr 1l:: : 1 1 "*111,,
Calculate the degree of-indissociu' Solution. Formic acid is weak electrolyte and
![on aru) concentrqliot of Hro+ ions 0.01 M ionizesinwater to give Hro+ ions accordingto the
sohLtion oJ'fomtic acid. Ka = 2.1 x 10-a tt 29E K. equation
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EQUILIBRIUM lt (ONtC EOUILTBRtUM rN SOLUTTONS) 813
-
HCOOH + H2O + H3C+ + HCOO-
Thus K, : 0.01@ x 0.01a
Let c be the degree of ionization. Then thc 0.0r
(1)nccntrution trI the vari0us species present al =001 xa2=2.7xlOa
cquilibrium would be as under: [K, = 2'r x 1o-4, givenl
HCOOH +H2O H3O+ + HCOO- . 2.1x l0-1
or dz=-;;=2lxr0-2
lnitial conc. 0.01 ---------\ 00
Conc. 0.01(r -a) 0.01a 0.01a
.. Degree ofionisation, a
at eqm. = 0.01 = '6.1x 10-z : 0.14
Concentration of H,O+ ions
[ .' c is very small and can be neglected
in comparison to 1l =C@=014x001
= 1.4 x 10-3mol L-l
l. Cnlqulale the degree of ionization and [fl3o+lof is the ionizntion coDstant ofacetic acid ?
2'
IA
Cmoll-l
InitialcoDc. 0 0 3. ds in Problem 2,
At.eqm. C(l -a) Ca Ca n 2 t -- 2
.,
A"=
Ca.Ca CaZ 4=i+ l 8x to-5 ='i' T - "'
ie.
el'i=Zl = T:7
o, ,,=y'ill-ioT=,1 24x 1o-3
7(, dissoqation = (4 24 x ro-3) x 100 = 0 424
l , 2. If the concentration of common ions in the solutions of two electrolytes (e.g: OH- ion concentratioD in
Ca (OH)2 and Ba (OH)2 solulions) is same, lhen on mixing them there is no changc in thc dcgree of
dissociatioo of either of the electrolytes. Such sdutioos are called isohydric solutions.
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Bt4 Pt a,lccr's lqerl coarse Che-isirlUIIU
An acid l.r
Throughout the history of chemistry, various
acid-base concepts have been proposed and used.
In this section, we shall bricfly discuss the different Examples. Substances like HCl, HNO, and
concepts put forth ftom time to time. Each of these
HrSOo, containing hydrogen, when dissolved irr
can be appliod with advantage in appropriate cir-
cumstances. In a given situation, the chemist uses water dissociate completety into H+ ions and the
the concept that suits his purpose best. negative ions as follows :
(1) Classlcal Concept of Aclds and Bases. HCI H+ + Cl-
The earliest classification of substances into acids Walcr
and bases was based upon the characterlstic HN03 H+ + Not
properties possessed by each one of them. For
Water
example, H2S04 2H+ + sol-
Acid was defrned as a substanc€ whose
aqueous solution possessed the following charac- Such acids are called strong acids.
teristic properties : Substances like acetic acid (CHTCOOH), car-
(i) conducts electricity, bonic acid (H2CO3), phosphoric acid (HrPOn),
(r'i) reacts with active metals like zinc, mag- etc., when dissolved in water dissociate into ions to
nesium etc. to give hydrogen, a small extent. Thus an equilibrium is set up be-
(iri) turns blue litmus red. tween the ions and the undissociated molecules as
follows :
(iv) has a sour taste. R Water
cH3cooH + cH3coo- + H+
EE
(v) whose acidic properties disappear on
reaction with a base.
AR
Wate!
Base was defined as a substance whose HzCO3 <- 2H+ + COl'
C
terlstic properties :
H3Po4 <.... 3H+ + Po?-
N
is
Hence we generally represent it as OH - (c4). Thus from the following reactions :
S
sented as
Na2 CO3 (s) + H2O +
HCI + Water ...--. H+ (aq) + Ct- (a{)
IIT
An acid is deJined as a substunce which has the as$'ell as a basc and hence is callcd amphoteric or
lendenc! to give a prolon (fl+ ) md o base ir amphiprotic.+
deJined us a substance y'hfuh has a lzt denc! to (r,) The reaction (c) above indicatcs that
tocept a proton, In other words, afi ocid Ls a proton Bronsted- Lowry definitions o[ acids and bases are
donor vhercus s bqse it a proton acceplor. not restricted to aqueous solutions. In this reaction,
HCI is acid because it gives a proton and NH3 is a
The above definition may be explained with
thc help o[ the lollowing cxamples :
base because it accepts the proton.
(ul) The presence oI hydroryl (oH-) groups
(a) HCI + HrO . . H3O+ + Cl- is not essential lor [o act as a basc. Thc
a substancc
only requirement is that it should have a tenclency
(b) CH3COOH + HzO + Lo accept a proton.
H3O+ + CH3COO- (r,ii) The above reactions indlca[g that a sub-
(") stance acts as an acid i.e. gives a proton only when
NH3 + H2O <- NHl+ + oH-
unother substancc to accept the proton, i.e. a base,
(d) Co3- + H2o + HCot + oH- is prescnt. For example, acetic acid does not act as
an acid in benzene solution because tbe latter does
(r) HCI + NH3 + NH4+ + Cl-
not accept the proton.
Thc following important rcsults may be (viii) The reverse reactions arc also acid-base
derived from these equations: reactions. For example, in reaction (a), in the
(i) HCI and CH3COOH arc acids bccausc revcrse process, HrO+ cangive a proton and hence
they donate a proton to HrO. is an acid while Cl- can accept the proton and
(il) NH, and COI- are bases because they R
hence is a basc. Thts there are l.wo acid-base pairs
EE
in reaction (a). These ure HCI-Cl- and
acccpt a proton from water.
H3O+ -H2O. These acid-base pairs are called
AR
(ii) Not only molecules but even the ions can co jugqte acid- bosepal)s. Obviously,
C
is acting as a base,
N
rcactions, water is donating a proton and hcnce is The conjugate acid-base pairs in reactions (a)
acting ils an acid. Thus water acts both as an acid to (e) may be represented as follows :
Conjugate Pair I
Acid,
t
Basc,
Conjugate Pair II I
Acid, Base,
,.Note. According to this concept if t*o acids (rvhich are acids with resPect to water) are mLred, the
rveaker acid will act as a base with respect to the stronger acid c &
.Anrphotcric is a gcncml tcrm fo! a substance acting as an acid aswctl as a basc When a(id base behaviout is rcslrictcd to
protorr lransfer, it is caUcd amPhiFotic.
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EQUtLTBRtUM [ 0ONlc EoUlLlBRluM lN soLUT|oNS)
-
HCIO4 + H2SO4 H3SO4+ + ClO4- ln acid ir defined os substsnce (ulom, ion or
Acidl Base2 Acid, Basel moleule) which is capubk ol acccpting a pair of
(Pcrchloric acid) eleclrons and a base is defued as a suhstance which
Thus HrSO. is a amphoteric or amphiprotic. is capoble ol doratiag an unshared pair of
ebttrons. In othcr word,t, un acid ir an electron pair
Adyantages of Bronsted-Lovvry concept oYer acceptor while u basc is an electron pair donotz
Arrhenius concept :
(i) Bron-sted-Lowry concept is not limited to Obviously, the reaction between an acid and
molecules but includes even the ionic spcies to act
a base, according to this concept, amountsto the
formation of a co-ordinate bond or dative bond
a.s acids or bases.
bctwcen them.
(ri) It can explain the basic character of the
Examples. (i) Reaction befiecett BF.' utttl NH., :
substances like NarCOr, NH, etc. (which do not
contain OH- group and hence were not bases
:F: H
accordingto Arrhenius defrnition) on thebasis that
.x .
acidic oxides like COr, SO2, SOj etc. and thc while BF, (inwhich boron atomhas only 6 electrons
C
basic oxides like CaO , BaO, MgO etc. which take in the outermost orbit) can accept a pair of
S
place even in the absence of the solvent, e.g. electrons, NI{, is a base and BF, is an acid.
N
+ SO, '----
IA
H
Obviously, there is no proton tratrsfer in-
H-N: + H+ .*
I
volved in this reaction.
(fi) Substances like BFr, AlCl, etc., do not I bwis acid
(iv) Reaction between CaO and SO, capable ofgiving an electron pair has the tendcncy
2- to accept a proton. For example, consider the reac-
tion
l ,- :o: o
Ca+ t): I + S: O :O:S:O:
l , O," -Ca2+ o:
l-Ewis acid
(v) Hydration of metal ions base. However Brcrnsted acid mqy not be o Lewi,t
acid. For example, in the above case, HrO is
,.H Bronsted acid because it is giving a proton but is
nlr+ + 6: O( -------
lAl (H2O)613+
kwis acid \H not a Lewis acid because it is electronically satis-
Irwis base hed.
TDes of Lewls Bases. Lewis bases can, ob- Usefulness and Limltatlons ofLewis concept
vioudy, be of two types. These are : No doubt, Lewis concept is the Eost general out of
four types. These are : (i) Lewis concept is so general that it con-
AR
(i) Molecules having a centrul atom with in- siders everyreaction forming a co-ordinate bond to
C
F CI
N
out of all but still Arrhenius concept continues to We put K [HrO] = It, called dissociation constant
be most important io explaining a number ol
phenomena. ofthe acid. Thus
lA-l IH3O+l
\ = tHA]
Diss<
Alternatively, we write
Acids like HCl, HNO3 and HrSOo when HA + aq <-- H* (aq) + A- (aq)
dissolved in water dissociate almost completely [H+ (aq)llA- (aqtl
thus producing a large number ofH+ ions. Hence 6=
these acids are called strong acr'ds. On the other
" IHAI
hand, acids like CHTCOOH, HF, I{2CO3 , Krowing the value of the dissociation con-
stant of the acid, \ and the concentration (C) of
HrPO. etc. dissociate only to a small extent in the
the weak acid HA taken, the concentration of
aqueous solution giving sriiall amount of H+ ions HrO+ or H+ (a4) in the solution can bc calculatcd
and hence are call ed,wesk acids. Similarly, bases
as follows :
like NaOH and KOH dissociate almost com-
pletely in the a HA + aq +H+ (qq) + A- (aq)
number of OH Initialconc. CnolL-l 0M 0M
whereas bases Corcs. at eqm. (C-r) M .rM xM
etc. dissociate only to a small extent in the ... * - lH+ (a(tl llA- (aqll _ x xx
aqueous solution and are, tberefore, called weok " tHAl C -x
bases. As usuallyx is very small as compared to thc
Thus the dissociation of weak acids or weak initial concentration C,r can be neglected in com-
basesinwatercanbereprcsented asan equilibrium parison to C. Hcnce the equation is simplihed to
R
EE
process. For example, the form
HrO+ J
CHTCOOH + CIITCOO- (aq)+ HtO+ (oq)
K,=i o, x=,/qFe
AR
NH3 + H2O
<-------\ NH4t @q)+ OH- (sO erc.
C
HA, its dissociation in water can be represented by parison to C and the equation has to be solvcd as a
IA
the equilibriurr
quadratic equation to get the value of.r.
IIT
Thus Ko values give a measure of the relative lH+ (aq\l lA- (uq)l
, -
IIT
Thus lhe relaliye strcngtht ol two acfuLs ol equi It must be remembered that since the ioniza-
moldr concenlration cfln be compared by t*ing tion of an acid or a base increases with dilution, the
squane flNl o! the rafio of lheir dis:sociation con. strength of the acid or the base increa-ses with
stanls. dilution.
Note that K, and Kb are taken as dimen-sion-
e.g K, for CHTCOOH = 1.8 x l0-5
less quantities (as already explained in unit 7) be-
K" for HCN = 4. 9 x 10- lo cause the standard state concentration of all the
species involved is taken as L mol L-1.
Strength of CH, COOH 1.8 x 1o-r
= Polyprotic acids and Polyacldic bases. Some
St.e,Uth.f t{CN 4.9 x 10-ro acids like sulphuric acid (HZSO.), carbonic acid
= t/3{ii " to, -- L.gz x tG = tEz (HrCOr), oxalic acid ((COOH).), phosnhoric acid
(H3POa) etc. contain more than one ionizable
Hence, CHTOOH r's neqrly 192 times sionger
than HCN.
proron. Such zctdB :trs-1qtreil polybasic or
For example,
Similarly, the relative strengtbs of two weak two steps as
bases of equimolar conccntrations can be com- -
foilb-ws':
pared by taking the square root ofthe ratio ofthcir
dissociation constants, i. e.,
., HrX (oq) + H* (aq) + HX- (aq)
ptrength of base (BOH), \A,/nx- lrqy + )r
w Strcngth of base (BOH), =\/tr
Ko,
EE
R
H* (aq) +
Thcir ionization constants, K,r and I(o, called
@q)
where \, and IQ, are the dissociation c.nstants of (he first and the sccond ionization con^stant respec-
AR
(K6l ofsome \itJk l)ascs xt f,9sK The overall equilibrium may be btained by
IIT
It may be noted from the above table that strcng acid (H3O+) has the weak coniugate base
4,,K,,,K., (II2O). To sum up
Similarly, polyacidic bases also ionize il steps I stpng qcid has d wmk coniugate base md vbe
with ionization constsnts Krl Iqr , Kr3 etc. ,!ry4a.
'
According to Bromted'l,omf concePt, the R
Thus the relative strengths of some acids and
EE
relative strengths of two acids are compared by their conjugate bases may be represented as fol-
comp to donate Protons. lows :
AR
comp tendencies to accept Acid : HIO, > HNO, > HF > HCOOH>HCN>H2O
S
protons.
Con- IO! < NOz- < F- <HCOO- <CN- <OH-
N
jugate:
two bases involved in the two acid-base conjugate
IIT
Base :
pairs can be found out if we know whether forward
Strongest
ieaction is favoured or backwatd reaction is
favoured. For example, consider the reaction
R
EE
AR
C
combines with four H2O molecules surrounded tcrrahedralty and exists as H9 Oa+ ion (H + + 4
N
H2O ...-
IA
Hroo*)'
IIT
60 9.6 x 10-la
Equation (ii) maY be rewritten as
arut OII- iorts (or H+ iotts stul OII- ioz't), But at 298 K, we know that
AR
The dissociation constaot ofwatcr, as givcl [ry 11,', = [HrO+l toH-] = 1.0 x 10-14
C
ctrn. Gi), cao be calculatod by subslituting th' .' [Hro+l [H3o+l = 1.0 x 10- r4
S
or lH3Orl2 = 10 x 1'0-14
IA
K=
55.)J = ot [H3O+l
N,iG cariiuily- that dissociationr'ionizatiol =10xl0-7moles/litre
constanl of water (K) is diflerent from ionic Thus in pure water at 25oC,
product of water (K,). The two are related as x l0-7M
lH3O+l = toH-l = 10
K
*= 15; or K*=Kx55 55 8.8. H3O- ton and OH- lon Concentrations in
Aqueous Solutions ol Acids and Bases:'lr' 'r"
Further, it must be noted that ionic procltrct of
waler is constant oDly at conslant lempuraturu lt" As already explained above, for pure water at
vulue at 25'C (298 Kiis found to be 1 008 x l{)-r{ v)8 K
However, for simpliciry, the value of K- at 298 K is lHjo+l = [oH-l = 1s-r ]\4
usually taken as
Now, if some acid (say HCI) is added to the
K*= 1oox 10-u pure water, then
Effect of t€mPerature on \' The ionic [H3O+l > 1o-7 M
However, experiments show that the equation
X* = [HrO+l IOH-I is still valid Thus the
[OH-l decreases and may be calculated
as
K_
[oH-l = ------ -
rnolecules dissociate into H+ (or HrO+) ions and
OH- ions. Thus the concentratiou of H+ (ol
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EaurLrBRluM (oNtc
- tr EQUILTBRTUM tN SOLUTTONS) 8115
Again, if some base (say NaOH) is added to method of expressing the H3O+ ion concentration
pur€ water, then
in terms of pH The symbol has been taken fiom rhc
loH-l > 10-7 M Danish word potea z de hydrcgen inn which nreans
But the equation Kl., :
[H]O+l [OH-] is still power of Hydrogen ions. The following diffcrent
found to hold good. Hence [HrO+l decreases and definitions of pH are used to exprcss the H1O+ ion
may be calculated as concentration.
K (i) pH oI d solutim is tl{rned us the magnitude o!
tH3orl =ffi tha negati"e pover to which lO trust be raired to
Eprsrs the hldtonium ion (H!O+ ) Lnnrzrtmtion*.
The increase or decrease of the H3O+ ion
conceotration in an aqueous solution of an acid or Thus ifin a solution
a base may be explained qualitatively on the basis
of Le Chatelier's principle (or common ion effect)
lHro+; = 16-' .'.(r)
as follows : pH=x
2H2O i- H3O+ + OH- However, this definition can bc used onlv
where the lHrO+l can be expressed as a powcr oi
Ifsome acid is added to pure water, HrO+ ion
10. In many cases, it may not be easy to do so, c.g ,
concentration increases, therefore the equilibrium a solution may have [H3O+l = 2.5 x 10-i N{.
shifts in the backward dkection (or ionization of
HrO is suppressed). Thus the OH- ion conc€ntra-. A more general definition may be arrivecl ut
from equation (i) as follows :
tion decreases. Similarly, ifa base added, OH- ion
concentration incrcases. Again, the equilibrium Thkinglogarithm ofboth sides ofequation (i),
R
EE
we get
shifts in the backward direction (or the ionization
of HrO is supprcssed) and hence the H3O+ ion log [H.0+] = log 10-'
AR
or
N
[H3O+] and [OH-] is always 1.0 x 10-14, the con- (iii) pII nay also be dcfined as logarithm oJ the
centration of H,C)+ ions mayvaryfrom 100i.s. 1M reciprocal ol H ,O+ ion concentration.
to 10-14 M. Thus a solution may have [HrO+l pH scale : Thcoretically, a solution m:ry lr.rr,
= 2.5 x 10-5 M or which may be writteD as any HrO+ ion conccntration and hcncc may ha\e
0.000025 M. Obviously, such a method of express- any pH value. Horvever, pructically, the solulionr
ing thc H.,O+ ion concentration is quite cumber- having HrO+ ion or OH- ion concenlration morc
sonre. Sorensen, in 1909, suggested a convenient than 100 ( = 1M) and hcnce OH- ron or HrO+
'srriclty scaking. iD ptacc of nrots. Goncrtrtrationr, acriviries of H+ ioru (rH+;";. I1.".;., r] l.*
the two arc cqual. "nr".nrrariorr.
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8i 16
Netl Coutse Chenristrg
ion conc. less than 10-11 l'{ are not common. This decreases enormously, Hence the pH range is
is because such solution's are not easy to obtain and taken as 0 to 14 for most of the practical purposes.
moreover as the concentration increases, the de- The acidity or the alkalinity of a solution may bc
gree of dissociation of the acid or the base represented on the pH scale as follows :
NEUTRAL
0'l 910 11 12
pH
F- + H2O <- og- +nr' (irr) A 10-8 M solutiotr of acid can not havo
pH = 8. The value will be close to but < 7 (see
- loH-l lHFl
^D -
(iD iolved example under'Tlpe VIII'page 8/26).
tF-l Messurement ofpH. Though accurate meas-
Multiplying eqns. (i) and (ii), we get urement of pH of a solution is done with the help
K, x Kb = tH+l toH-l =K? of an instrument, called pH-meter, approximate pH
v
(within the range of 0'5) can be determined with
I fr,xf.o=fv i
pll papers which show different colours
the help of
when dipped in solutions of different pH.
log Ko + log Kr = log K,
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EQUTLIBRtUM
- 0ONtC EQUtLIBRTUM tN soLUIoNs) 8117
IYPE I. Orl thc cslculatlo! of IHrO* ] and IOH- | 0 2 M sodium scetate. Givcn thqt the ionization
(K) lot acetb acid is I . I x 10-s,
constsnt
, I \ \\l!,1 \' 1 Calculate tlrc H3O+ and OH- Solution. Acetic acid ionizes to a small extent
ion concettrations at 25" C in wherEi-as
soclium acetate (being a salt) ionizes com-
(i) 0.02 N HCI solution pletely. Suppose acetic acid ionized at equilibrium
(ii) 0.005 N NaOH solution
: r moles. Then
CHICOOH+H2O ;:==l ggr699-agr6+
!4,1S1. (i) HCI completely ionizes as
Initial
HCI+HzO ,H3O+ + Cl- 0.02
moles
... [H3O+] : [HCU Moles 0.0?-x xx
: 0.02 N (Given) at eqm.
: 0.02 M cHrcooNa ...-r 9111699- .,r- 1r1u+
. HCl is monobasic)
( Inirial 0 z 00
= 2x10-2M moles
Now as [Hro+] [oH-l : Kr" = 1o-ra Moles 0 0.2 0.2
K l0- t{
at eqm.
' IoH-l = = Zx 10= Thus in the mixture solution
trptl R ICH3COO-] = 0 2+ x =O.ZM
EE
= 5 x 10-r3M
(il) NaOH completely ionizes as (CHJCOO- are obtained mainly from
AR
= 5x1o-3M
IIT
lcH3cooHl
Now as [Hro+] [oH-] = Iq = 10-ra
0.2 x [H3O+]
.'. lH:o*l =
. K, l0_r4 18x10-s=
lrr_| ,x ro= = 0.02
T,ROBLEM9 FOR
lf hydrogen ion concentration iD a solurion is 1 x 10-5 moleMitre, calculate the concentration of oH - ion in
this solutior (K,y = 1O-l{ moles2 / titre2) [Ans. 10-9 mole-s/litrel
Note. Since the calculatioa of HrO+ iou concentration is tsually the first step towards the calculation
of pH, therefore the numericals of this type are automatically included in the various
rypes that follow.
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8^8 N e.4
Uog3 10-21
Concentration of HNO, solution
=- +
S
=- (0.477L - 2) = 1.s229
IA
K.?
(n'i) HrSOn completely ionizes as = 6.3 g per titre = motes/lirre
f;i
IIT
FOr< iF?.RA@1Ii:li6,E \
l. "ROBLF,lvi,I
Calculate the pH value of 0.001 N HNO3 solution 3. What is the pH of a sotution whose H+ ion con-
[.\ns. 3l cenkation is 2 x l0-5 g ions/litre ? I{ s. 4.699]
2. Calculate the pH value of lO-3 M HCI solurion 4. 0.049 g of H2SOa is dissolved Per litre of the giveD
nDs. 3l solution. Calculate the PH of the solution.
hns.3.01
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EAUtLtBRtUM I (ONtC EQUtLtBB|UM tN SOLUTTONS)
- 8/19
5. Calculatc tbe pH of a solution whicb is I x 10-3M 7. Cakllate the pH ydlue of a 4.9 x 1O-a N
with resp€ct to sulphuric ac.id. monobasic acid solution assuming
JAns. 2.5tDl tioo.
6, 13.5 I of an acid HA, of rDolecular mass 135 was t. Calqrlate rhe pH ofa solution obr
dissolved in litres of aqueous solu tiorl Calculate
IO 25 rd of Nn 0O HCI ro 500 ml.
the pH of tbe solurioD, as miDg thc acid to b€ 9. I ml of 13.6 M HCI is dilured with give
completely dissociatcd. I.r.tts.2l 1 liue of thcsolution. Calcutaie pH o li.ing
solution. .Gjt
'Hi.lilN,T9
4, tll2so4l = o
qof,e n,or l-1 =5x
'lo-a M. E. NrVt = NzV2,25 x 1 / 100 = N2 x 500
+o
IA
NaOH -------- Na+ + OH- (ii) Colculation of the OH- ion conc.
IIT
?R,ACTICE
l. Calculate the pH va MNaOH(6) 3. must be
0.01 M NaOH
' "c. and H soturion'ai iB N/10
D G) t2.6ol
2. Calculate th€ pH ofa solutbD contai gcaustic
soda/litrc of uater, D.69ryl
!rns. 4 g, 131
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8120
4, C3lculate the PH of thc following solutions : aod hydroryl ions and the PH of the soluiion'
mnde (Atomic mass otsr = 87cdot6) (N C'E'R'T')
[ose Amourlt dissolved voiume ofsol.
(a) noH 2s 2L 1sl+; - o.rstt u, [oH-l = o'3152M'
". pE = 13.501
(b) ca(oH), 0 3I 5OO mL
6. If 0 .561
I KOH is dissolved in water to Sivc 200 mL
(c) NaOH 0 3I 2Il0 mL
ofsolution a]298 K calc'ulale the co[centration of
(Atomic masses : 1'l = 2O4, Ca = 40, Na = 23) potassium, hydrogen afld bydro]ry| ions. What is its
(N.C.E.R.7:.) [,r,.. (c) 11 70 (D) 12'21(c) 12 s7l inz (N.c.E.R.r.)
lenr. tK+l = toH-l = o'o5M'
solution. Calculate the concentratioos of strontiunl lE+I = z'o x 1o-r3 MI
[oH-l = 16'22x1o-3
= 2 x [ca(oH)2]
- [Hro*] = -19-11, =2* 16-r:.
.1 pOH - - log(16 22 x i0-3)
pH = - log 12 x 10-13; = 3 - 7'2101 = l'19
3. ForLof I N NaOH solution, NaOH dissolved =
1 :. pIJ= 14 -POH = 14-179=1227.
18eq. =408 R
6.tKoHI =+x#r=oor0M
EE
.. For I L of N/10 NaOH sol., NaOH dissolved
AR
KOH K+ + OH-,
=qo x#=rs As
-
...
C
[K*)= {oH-]:0.05 M
{oH-l = 10-r M lH+l = Ky,/[oH-l
S
N
= 2.0 x 10-13 M.
IIT
pH=-log10-13=13
IL' cHlcoo- ion and onc H+ ion or l-lrtl' ion j cH3cooH +H2O <--r cH3coo- +H!O+
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EOUTLTBBtUM
- (tONIC EOUtLtBHtUM tN SOLUTTONS) 8121
1.8 x 10-5. Calculate tbc pH\alue ofthe decjoor. solurioD of lacticacid CH3CH (OH) COOH. What
mal solution ofacctic acid. I Ans.z.t7J is the pII of the sample of milk ? I(, for lactic acid
2. A0.05 N solution ofaceticacid is found to be 1.97,
at 25"C is 1.37 x 10-4.
ionized ai 25'C. Calcutate (0 Iq for aceiicacid and
(r'i) thc pH ofthe solutioD. | ,. .2.431
5. Calculate the pH of 0.15 M solurion of hr?o-
I Ans.u) l.E x 10-l (ri) 3.02231
3. Calculatc the pH value of a solution of 0.1 M chlorous acid HCIO (Ku = 9.6 x l0-7).
NH, (K5 = 1.8 x lo-5) l2l I ars.1l I 3.421
[0.es46 4l - H+ ,, ,,
tains
ffi = 10-a mole
S
= 3.0454 = 3.05 =
N
N HCI withpH =
IA
MS FCR \; :
1. Calqrlate the PH of a solution obtained by mixing 3. Calc-ulaic thc PH vsluc of I mixture cf,rtoinlnS 50
50 ml of 0.2 M Ho with 49.9 ml of 0.2 M NaOH ml of I N HOand 30 ml of 1 N NaOH solutioD'
solution assuming both to be completely dissociated.
Ans. 0.602U
[ tu,s.3.699] I
thk temperorure.
= 3.09 x 10-7 M
S
K, lHlo+l lA-l
N
10-
=t"p=l =,=t
11
v:
.. -:----=-------,
toH-l
IA
[HAI
IIT
2. The pH of blood serum is 7.4. What is the hydrogen fur citric acid b 8.4 x tO-' mole/itre, lYhat is thc
ion concentration of blood Eerum ? conctntration of citric acid in lemoniuice ?
t. 0.01 M solution of an organicacid is found to have and its dcgrce of ionization in rhe solution.
a pH of 4.15. Calc.ulate the conc€ntratior of the (N.C.E.R.T.)
anion, the ionizrtioo constant of the acid and its
I u,s K, = 2.09 x 10-4,.z - 0 0{s7l
PK.' I n!ls. [A-l = 7.0E x 10-3 M,
11, Calculate the hldrogen ion concenration in the fol-
IL = 5.0E x to-1, pKo = 6.29l whce pH are g rn below
lowing biological fluids :
9. The pH ofo.005 M codeine (ctsH21NO3) solution (4) HumaD muscle-fluid, 6 83
is 9.95. Calculate its ionization caNtant aodpKD. (b) HumaD stomach fluid, 1 2
(c.) H-uman blood,7 38
[ \,,..K, = l
s.tl 6 x 10-6,pK, =
(d) Humansaliva'6 4 (N'cER'7:)
10. ThepHof 0.1Msolurionof cyanic acia lucNo;
is 2.j4. Calcutate the iooization constanr ofrhe acid | \r',.(a) t 46 x t0-7M(r)0.063(c)4.17 x t0-8M
(d)398x10-71
9 Y29 x lo-r
K. = r"ilE:ii_,r
PK, = .-loBK,= -log(5 oE x:o-7)=6 29.
(7.943 x 101(7_.943 x 10-1
8.4 x 10-4 _ 9. Codeine + water codenium ion + OH-
=:=+
From given pH, [H+] = r.12 x 1o-10 M
or [HCit] =? s x1o-2M
5. pH = 4 mcals [H*] = 1o-o M .. tOH-l = K-l[H+] = r.e3 x 10-5 M
HA+H++A- K, = rBiJSoJf_r
Ar eqm 1- 10-a - 1M t0-1M 10-4M
(8 93 x -5)2
lO
to-ax1o-a=ro-a 1.6 x 10-6.
O_
r0. HCNO i.l H+ + CNO-
7. RCOOH <=- RCOO- + H+ pH = 2.34means - tos IH+l = 2.34
lH+l - [Rcoo-] - ,o-, M
1... ,u = ry or log [H+] = - z
=a.66
?,4
=-[1.M14-8] .
1..\ \\l l'l-l,l l.,l cnt3 of 0. 0 1 N HCI is added to
AR
1. 1o-6 M NaoH solution is diluted 1000 times cal- 3. The pH of a solution is 5. Its hydrogen ion c.D'
c€ntratioD is increas€d 100 times. What is the PI{
culatc thepH ofthe dilutcd base.
of the resultifl8 solutiou ? [/\ns. 3.01
I,\u\ 7.04541
2. Whatwill be thePH ofthe resulting solution if to a
100 ml of HCI solution ofPH = 1 0, 900 ml of
distilled water is added 'l 201I
HINTg FOROIFFICUUT ?ROOLEM-9
.. pH=2
1. After dilutioD,
[oH-l - 1g-a y. HeDcp [oH-]
3.
fiom H2O cannof be ncglccted. pH = [H+] = 10-5 M. on iocreasing
5 means 100
2. l0O mlba! bccn dilutcd to lfi)O mt. Hencc dilution tinres, new [H+l = 1o-3 M. soPft = 3'
i. For a neutralsolution,pH = 7 at 298 K (25'c). With increase in temp€rature, as dLssxiation of HzO molccules
incteasesie. [H + ] and Iotl - ] increa,se, so the ionic product iocreases with increase of remperature. Fur(bcr,
as IH+] increases, pH decreases with increase of temperature.
A few interesting results are given beloff :
(i)Ar273K(0"C),K,=10-l5sothaipHofneurratsotutionarthrsremperarure=T.5andpHscaleis0to
15.
i L PH of the solution of a weak acid or a weak base depends upon its degree of ionizrtion (a). The relatiooship
IA
HA ._r H++A
Initialconc. C
Conc. at eqm. C(l -a) Ca Ca
lH+l=c" :. pH= -togtH+l = -rogCo. Bur Iq= aoz o, g=I\taz
pH = - tog (Ko/ a)
I. Salts of lyeak acid and strong base ; The hydrolysis constant (Kr) witl, therefore,
(a) Hydrolysis constant. Representing the be given by
salt by BA as usual, the hydrolysis may be repre-
sented as follows :
,, toH-llHAl ch .ch chz
" tA-l c(l -/r) t-h
BA + HzO . - BOH + HA IfI is very small as compared to 1, we can take
salt srrong weak
J t- 1 - /r = 1 so that the above expression becomes
Kr, = G)
tA-l
/,=lF
IIT
.by (iii),
_ .Multipllng
equation (i) wirh (,r) and dividing
rH.t=?q
we get
Kr, L IoH-l tHAl [H*] lA-l lH*l =
K* tA-l " lHAl ( \'. pH= -log[H+] = -log
1,
X-:l
tHrl IoH-1 = -r"* (55)'"
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Pradeep's
p" = lI- log \ - log K, + log cl Substitutiug the value of Kr, from equation (r),
we get
pH = pKa + los cl
+bK- +
...(rr)
At 298I!pK. = 14.Hence at298 K, we have
I (c) pH. ln this case we have
pH =7 + i [pK" + logc]
B+ + H2o <----s BOH + H+
Thus knowing the molar concentration c of
origiDal conc: c 00
the solution and the dissociation constant K, ofthe Conc. at eqm: r (1 - l,) ch ch
we get
Il. Salts of strong acid and weak base :
(a) Hydrolysis constant. For the salt BA, thc
hydrolysis may be represented as
BA + H2O + BOH + HA
,H.'=c
R
€=rs=(Yj)',,
sak Wcak Slrong
EE
Ji '"
or A- + Hzo i-----r BoH + H+ + A- :. 'l *',l
=-,"rf5t:'l
AR
B+ + pH=-log[H+l
or +H2o + BoH +Ht
C
B+
S
lBoHl lH+l
|] - :__------:-:----!
Nn ...(yii)
[B+l As before, this equation can be rewritten as
For the weak base BOH, the dissociation
equilibrium is eH::bK*IpK6 + loscl
BOH i.------: B+ + OH-
At KPI!" = 14. Hence at 298 K, we have
..
The dissociation coostant K, of the weak 298
__
.,,, _
[BoHl [HAl
...@ii)
Kt=h2
[B+l [A_]
For the weak acid, n=.&,= (ru)
HA i- H+ + A-,sothat
(c) pH. For the weak acid HA,
-.(nv) HA H++A-
For the weak base, -rlH*llA-l
BOH <- n* + OH-, so that
- [B+lloH-l
,.b _ ...(:v)
or [H+]=,..#l- =K";T*6
IBOHI
Also, we know that t
=r.1-h
Kl, = [H+] [OH-] ...(rvO
Multiplyi'rg equations (rii), (.riv), (xv) and But from equation (xviii),
dividing by equation (rvi), we get
f7 = r'( to tr'at we have
Kr, & Ka
=1
K,/
tH*l=K,/q =x,/Rk
...(xyri)
R -.ffi
-Y-K-
EE
(b) Degree ofHydrol;nis.In this case, we have
pH=-log[H+l =-l"s\ry
AR
. lK"K-l
@nc. :
=_,*l ,
S
ch
IA
at. eqln. : ,l
__
IIT
tBoHl [HAl
.y - or pH = -j tr"c r" + log re - log Kol
[B+][A_]
ch.ch * or this equation may be written as
= cTl : h\.;0 - D = 6r;5 -'1"''r
Here, the relationship between K, and i does
not involve c. Thus rhe degee of hydmtysis of uch o
ralt is indgpendent oI the concentralion of the solution. "';,2e8K;i;"
If /z is very small in comapri-son to 1, we can p.J=7+)Wx"-IiK,l
takeL-h = 1so that equation (.rvr'ii) becomes
IHCNIIOH-l rxr
K,,=-,6fi=t * =, - *- tog (1 6 x 1o-5) + log o 1l
-=,_,=;
nr, = & x i = v(r.6 x r0-5) (o.l) =t -)Us- o.o2o41) - 1l
=126x10-3
i.e. [oH-l = t'?5 x 10-3 =510
c l.\\\ll'{ I ''. Calculate the pH ol 0'01 M
K- 10-14
. tH'l = toH-l = t r6x lo-3 solution of NHaCN. Given that the dissociation con'
x KrIor
stonts are: Ko for HCN = 6'2 10-10 and
=1'94x10-12 NH, = 1'6 Y P-s.
pH = - log [H+] = - log (7 94 x 10-1'z) and
!o-!utrglr-. As NH.CN is a salt of we ak acid
= 12-0'90=11 1 weak ba-se
l,l\,{i\ I I't.|.. 2. Calculate the pH of 0 }0 M
sotution olNHoCl. Tlrc dissociation constant (K) ol = 1'0
NHris 1'6 x 10-s.
As NHoClis a salt of weakbase and
strong acid,
K*
*,=il=#=625xr0-ro
10-14
6"2 y 16-ro;66-rr
1.6 x 10-5
The hydrolysis reaction will be R /t{?5
EE
+ H2o <----r NHi + H3o+
NH4+ = 'r lo-r'g
AR
Initialconc. c M
eqm. c-x x x =7O-O79=9'21
S
At
N
prr=1+lan-o*ol
or, = q;; = v(6.25,,s-roy x o.t
= 7'9 x 10-6 M ++l-log\ + logK6l
=7
,.e. [H+l = 7 9 x 10-6M
:. pH= -log[H+] = - log (7'9 x 10-6)
x
=7+ los (6'2 1o-ro)
=6-0 90=5'10 +F
Alternatively, applying the form.ula directly + los (1 6 x 10-s)l
1
pH=7-ib\+toecl =7+ +(fi - o'7s2A) + (- 5 + 0 2041)l
1
1. Whatwould be thePH of 0 1 molar sodium ace tate hvdrol,rsis of aniline hvdrocbloride in I 0N solution
solutioD, EiveD that the dissociatioD oonstant of a[ 25'6. Aso calculaictherH of the solution.
aceticacidis18x1O-5 gns. t tTl [rrs.0 415%' 2 3El
3. At 25'C, the ionisatio[ coNtant of anilinium
2. The dissociation constant ofaniline (C5H5NH2) as
hydroxide is 4 6 x 10-10.'Ihking ionic Product of
a base is 5.93 x 10-10.The ionic product of watcr
water as Ir 10-11, catculate (a) hydrolysis con-
ar25"Cis 1 g2 x 10-14 Calculate the Perc€ntage
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EQUTLTBHtUM fl 0ONtC EQUtLtBRtUM tN SOLUTTONS)
- 8/33
stant of irniliDium chloride (D) the degree ot 6, Tho ioDization coostant of chloroacctic acid is
hydrolysis aDd (c)pH vatuc of0 2 nrolar solution
of the salt. I 35 x l0-3. What will he rhepII of 0.1 I\,t acid
[,\rs (a) 2.17 x l0-s 0.1 M sodium salt solutioD.l (N.C.E.R.,I)
aod irs
(b) 3.29 x tO-2 1c; l.tS;
[.\ur 1 94, 7 94]
4. The iooizatioD ooDstaDt of Dirfous acid is 7, C.alcularc thepH of0.05 M sodiunt acerate solu-
4.5 x tO-4. Calculate rhepH ofO.M M sodium tion rfrhepK, ofaccric acjd is 4.74.
l..\!rj t.721
nitrite soluiion and also its degree of hydrolysis. t. The pK.a of aceric acid and pKb of aD]moDiunr
(N.C.E.R.T.) hydroxHe are 4.76 and 4.75 respcclivcly. Catculal(
lAns.pIJ=7.h,a = z.:e x ro-!I the hydrob6is constant oi amntoniurrr acelare ar
S. A 0.fi2 M solution ofpyridine hldrochloric haspH 298K and also the degree ol h)ctrol).sis an(lpl I ot
= 3.214. Calculate the ionization constant of (a) 0.01 M and (r) 0.04 M sotutrors.
Pyridine. N.C.E.R.T.) [,\ns. I .5 x 10-rl l.\us Ki = 3.25 x 10-5,1 = S.7 x 10-3
sndpH = 7.00S (s6me in hcth coscs)l
toH-l = ,f;, c x
1ou-1 = 'rqr- = {-i" rotl lon+;
AR
d
=r's 88"10 =e 42x1o-1
=C;;=q,.", ='t.46x 10-6-
C
*"=;tlill,l?::'"1,
1u*r=ffi"=r34xK-e
S
N
127
IA
so concentration
of aratus used is
sh of the solution
is the helP o[ a
Dinelte) and the other solution is tukun in [h':
Lr.irette'which is graduated in cc's and has a stop- (2) They dissociate in aqueous solution as
colour.
IIT
BURETTE
STOPCOCK
TITRATION
FLASK
SOLUTION A red.
Phenolnhlhulein cqnnot ba us?d us indicator il
the buse is weak e.g NH.OH. This is because the
FIGURE 8'2. Apparatus for titration oH- iom produced from the weak base are in'suf-
ficient to ihift the equilibrium (i) towards right
Thcrc arc many t,?cs oI Iitrations such as
substantially. Similarly, nrcthyl orange is .not .a-
rcdox titrations (involving tlxidation and reduc- iuitable indicator if thi ucid is wesk\ke acetic acid
tion), acid-base iittrations (involving ncutraisa-
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EQUILIBRIUM II (|ONIC EQUILIBHIUM IN SOLUTIONS)
- 8/35
(CHTCOOH). This is because the H+ ions
produced are irxufficient to combine with the
OH- ions and shift the equilibrium (ri) towards
right significantly.
8.123. pE at the End-Point of Acid-Bas€
Tltrations. One often assumes that the pH at the litration curves of strong acid against strong basc
end point ofan acid-base titration must b;7. How- (e.9. HCI versus NaOH), weat acid against itrong
cver, we must remember that what we have at the base (e.g CH3COOH versus NaOH), weak basE
end point is an aqueous solution ofa salt formed as
against strong acid (e.g. NH.OH versus HCI) and
weak acid against a weak base (e.g CH3COOH
versus NH.OH) arc shown in Fig. 8.3(a), (D), (c)
and (d) respectively. The point at which there is a
sudden chalge inpH when a very small amount of
the titranr is added to the titrate is called point of
lnllection.
R 1
EE
pH
t
I
AR
I
C
o
S
o
N
IA
IIT
o
Volume ot HCI add6d in mt
Volume of0.1N NH4OH added in mt
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Neut Course Cfrcnt i stru
8i 36
howpH changes during acid- When 50 ml of 0' 1 N NaOH solutioo has becn
To understaod
ation of 50 0 adde AII
solution.The the a aCl
lutionmaybe only. has
sudd
Further addition of oven a very soall amount
Initiallv. as the solution taken in the flask is 0'1ml) increasos thepH of
of NaOH solution (say
0.1MHCiiH+l = 10-r, pH = 1 0. After l0 mt the solution very rapidly. This may be seen as fol-
of 0.1 N NaOH has been added, it will neutralize
lows : -
10 ml of O'1 N HCI so that HCI left in the solution
60 Now, volume of the solution
= rl0 ml of 0' I N and total volume of solution =
ml. To calculate normality of HCI in the final solu- = 50 + 50'1= 100'1ml
tion, apply Nrxvr=N2xv2 i'e 0'1x40=N2x60 0' N NaOH solution left unneutralized
1
0 loH-l =
N
10.0 118
20 .0 137
300 1.60
,IC,0 1 .96
490 300
4 .00
49.9
700 solution is added from thc buette.
500
E.12,,1. Selectlon of a sultsble lndlcator' The
50.1 10.00
indicator used should be such that it shows change
51 0 11 .00 in colour in the same pH range as required around
1196 the equivalence point. A number of indicators are
60,0
avaihLb for the entire pH range. These are given
700 t2 22 in Thble 8.6. below.
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EQUtLtBBtUtvt (ON|C EOUILIBRIUI\,4 rN SOLUTTONS) Bl37
-
T.A.RLE 8,6. Common acid-base indicators arrd ?.
,\ln _ lH+llln-l
_
their coloul. changes lHLrl
Indicator pII.range Acidic Alkallne The exact point of the colour changc will be at
colotlr colour thepH when lHDrl = [In-1. Substituting thisvalue,
we get
Methyl violet o-2 Ycllow Violet
Methyl yellow 12-2.3 Red Yellow Krn = JH+l or - Iog K,n = - loe [H+l
Methyl oran8e 3. 1--4.5 Red Yellow i.e. pKr" = ?H
Bromocresol 3.8-4.6 Yellow Blue
Thus for a particular, tittration, the indicator
greeD
selected should be such for whichpKrn = pH ofthe
Methyl red 42-42 Red Yellow
solution at the equivalence point. For example, in
Litmus 4.5--€.3 Red Blue the titration of HF with Naotl, pl{
at the
Bromotbymol 6 0-7.5 Orange Blue equivalence point is 8.1, pKr,, for cresol red is 8.1.
blue Hence cresol red should be uscd as indicator in this
Phellol red 6.4---4.2 Ycllo Red titration.
Cresol red 7 .2-8 8 Yellow Red E.12.6. Explanation ofthe pH range of2 units
of indicators. From Table 8.6, it may be seen that
Thymol blue 80-96 Yellow Blue
most of the indicators have a useful colour change
Phenolphthalein 8 3-10.0 (hlourless Red over apH range of 2 units. For example, the most
Thymolphthalein 9 ,3-10.5 Crlourless Blue common indicator, phenolphthalein, changes from
colourless to pink in thepH range from 8.3 to 10.0.
R
Aliza rin yello$, 10 1-12 0 Yello$/ rfiobt
EE
This solves the problem for the fact that we maynof
Tlinitrobcnzene 12 0-14.O C.olourlcss Orange have an indicator for whichpK,n is exactly equal to
AR
From the titration curves, it rnay be observed the pH at the equivalence point. Thc cxplanation
C
(i) For titration of a strong acid against a For the indicator HIn,
N
IA
strong base, any indicator out of methyl orange, HIn (44) <- H+ (aq) + ln- (aq)
IIT
- lH+llln-l
against a strong base like NaOH solution, only ,,
K'' ='
pheoolphthalein is a suitable iodicator.
(iii) For titration of weak base like NH.OH
tiinl- "'(')
Our eye can detect the change in colour if the
again-st strong acid like HCl, onlymethyl rcd canbe concentration of one ofthe colourcd form is at least
used as an indicator. 10 times greater than the concentration of the
E,12.5. To prove that for the colour change other. Thus (o see lhe acidic colour
pKrrrror. = pH at thc equlvalcnce polnt
lln-l _ 1
As already meotioned, acid-base indicators [HInl l0
are weak orgalic acids or weak organic bases. Sup-
and to sce the alkaline colour
pose we consider an indicator which is a weak
organic acid. Let it be represented by HIz. In lln-l _ 10
aqueous solution,it dissociates as [HIn] - 1
In terms of molarities, as
HA + H++A-
AR
or
N
rH.l=1X+K,
IIT
HA + OH- # HrO +A- Equation (ii) and (iii) are called molarity
At this point, tHAl = IA-l equations. These equations may also be uritten
:. pH = pKo - log 1 =pK,. as
8.13. Solubilhy Equilibrium and Solubility Produci Similarly, the solubility products of BaSO4,
If a sparingly soluble salt like AgCl is stirred Al (OH), and Car(PO)n may be represented as
rvith water, only a small amount of it gocs into
solution (and makes the solution saturated) while BaSt\ (s) <J Bo'* + SO?- ;
most of the salt remains undissolved. But \yhatever
little amount of thc salt dissolves, it gcts completely R (o = [na'z+1 1srlo2-;
EE
dissociated into ions. In other words, when a spar- Al(oH)3 (s) + Al3+ + 3OH-;
AR
At equilibrium thc solid AgCI continues to Ca, (POo), (.r) .* 3Ca2+ + 2PO3o- ;
N
IA
tAgcll
Since concenlration of the undissoiiated solid
remains almost constant, wc may wr;te
lAs+l [cl-l : K x [Agcl] : Ks,
The values ofsolubilityproducts ofsome com-
where \, is callcd solubility product and is equal
mon sparingly soluble salts are listed in the follow-
toionicproduct [Ag+l [Cl-] tbrasatxraredsolu- ing table :
tion.
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8l40 Neul Course Cltemistrg
'lAItt,D 1t.7. Soiubility products ofsome com- of Solubitity Product. The
mon sparingly solutrle salts at 29t K product of a sparingly soluble salt at a
temperature can be calculated from a
Salt ri.p is"rr I K* of the solubility of the salt in water at
that icular temperature. This is illustratedwith
AgCl l 8 x 10-lo SrSOa 3.2 x 10-1
the i of the following examples :
/\gBr 5,0 x 10-13 SrF2 2.5 x 10-e
7'1rc solubility of AgCl in water
AgI B 3 x 10-17 SrCO3 t I x 10-10 be 1.06 x 10-s motes per litre.
Ag2CrO4 l.l x 10-12 cds 8 0 x 10-27 the sohtbility product of AgCl at this
A!"SO. 1.4 x 10-5 CUS 6.3 x 10-36 . AgCl ionizes completely in the
A82CO.r 8lx 10-12 Hgs 4 0 x t0-53
BaSOa l 1x 10- 10 MrS 2 5 x 10-13 AgCl ----------- Ag+ + Cl-
mole of AgCl in the solution gives I mole
r'.e. 1
BaCrOa 1.2 x l0- lo Nis 4.7 x 10-5
of Ag+ ions and 1 mole of Cl- ions.
IJaF2 1.0 x 10-6 Pbs 8.0 x 1o-28 Now, as the solubility of AgCI
CaS04 9.1 x 10-6 SDS 1.(lx l0- 25 :
1.06 x 10-s moles per litre
CaqC)4 4.0 x l0-e Zus 1.6 x 10-24 ,1 [AC+l = 1.06 x 10-5 moles/litre
CaF2 5.3 x 10-e Fes 6.3 x 10-18
and [Cl-] = 1.96 x 10-5 moleVlitre
CuCl
r'. K.o for AgCl = lAg+l [Cl-]
CaCO3 2 8 x l0-9 1.7 x 10-6
Oa(Orl)2 55x10-6 H82Cl2 l 3 x 10-18
R
EE
Pbctz
= 1.1 x 10-lo
Cu(OU)2 2 2 x 7O-7o 16x10-s .Er,rrtt'1.t.- :. I'he sohtbility oJ Mg(oH)2 is
AR
.,u(oH)3 13 x 10-33 PbF2 77x10-8 835) x 10-3 gllitre at 290"c. Find out its K,pat this
C
lre(OtI)3
S
the {olution as
IIT
l. C€lculate the solubility product ofsilver bromidc if the solubility product coosiant at roonr tempera-
the solubiliiy of the salt iD saturated solution is ture. (At. wt. : Pb = 20'l, Cl = 35.5)
x tO-7 noles,4itre. l,rr. 3,25 x 1o-13;
.5.? [\rs 3.09 x 10-a]
A saturated solution of sparingly soluble lead 3. The solubility of lead iodide in water is 0.63 Mitre.
chloride on analysis was found to coDtaiD 11.84 Calculate the solubility product of lcad iodirle. (At
Mitre of the salt at room temperature. Calculate massofPb = 207,I = 127) [.tDs, 1o-81
x l0 'nrol L '
= 4.259
=309xl0'
PbCl2...- P5z+ 12 61-,
Ths results can be easily explained on thc This is again because by Le Chatelicr's prin-
basis oI Lc Chatelier's principle. ciple, increase in the concentration of Cll- ions
C
a
some solid AgCl separates out. Similarty, solubility
N
added to it.
To this solution suppose the salt of this woak Thus'common ion etlect'may also be defined
acid with a strong base (e.& CH3COONa) is added. as follorvs:
It ionizes almost completely in the solution as fol-
lows and provides thc common acelale ions Il to the soltttion of a b,eflk electrubte (e.9. &cetic
CHTCOONa .......; CH:COO- + Na+ acid or ammonia) , whi.h ionizd la a sn4U &enl,
a strong eledrotllc hr. a common ion k added
As a result, the concentration of CHTCOO- which ionizes alnust the ionizattun ol
ions increases and by Le Chatelier's principle, the lhg$e\k rased. Similorty,
dissociation equilibrium (i) shifts backwards i.e. if to the solution of a solthle salt (like
dissociation of acetic acid is further suppressed. AgCl, PbI2etc.), iI a common
(li) To the solution of the rvcak base, ion ir ailded, tfu sotubiliry of lhe sparingly tohtble
NH4OH, if NH.CI is added which providcs the sal further decreues.
commoo NHo+ ions, dissociation of NH,OH is sup-
Remembcring that the solubility product of a
pressed
salt is constant irrcspective of the source ofthe ions,
NH4OH + NH4+ + OH- thc solubility of a sparingly soluble salt in the
NH4CI + Cl- prescnce of a soluhle sall having common ion can
-NH4+
(iii) To the solution ofsilver chloride in water,
be calculated. (See solved example 3 on page of
8t44).
(being a saturated solution because solubilitv of
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8142 Prldeep's .;i
&lso ? (N.C.E.R.T,)
or Y=5X10-10
IA
,, _ lH + 12 ls2-l y=109x10-reM.
lH,Sl R
EE
P-Rpib.L.EM5 FOR
AR
C
1. The pKa value of acetic acid is 4.74. Calculate 2. Calculate lhe de8ree of ionization of 0.02 M
S
degree ofionization of 0 05 M acetic acid solution. dimethyl amine solution. GiveD that its ionization
N
How is the degree of ionizatioD affected if iLs solu- coDsiant is 5.4 x l0-4. What percentage of
IA
tioD is also (u) 0.01 M (6) 0.1 M in HCI ? dimettryl amine is ionized if the solution is also 0.1
IIT
[.lrrs. 0.019, (a) 0 001E (D) 0 flX)lE i.e. each case, M in NaOH ? [.\ns 0 164,0 00541
It decreases by o factor of10l
I;\.\!IPLIj t . Tlrc solubility product for silver wqter is 1.5 x 10-10. Calculate its solubitity in
EE
chlotide is 1.2 x tl-to s! 29E K. Calculote the 0 01 M NaCl aqueous solution. (Roorkee 1995)
AR
ing to-ihe-e[iration
N
AgCl (s) + AgCI (aq) + Ag+ (oq)+Cl- (aq) is s mol L-1, then from AgCl that dissolves,
IA
Let s bc the solubility of AgCl in moles per [AC*] = [Cl-l = .1 pol 1-t
IIT
litre.
.. Total [Cl-] =0 01 +s=0'01 M
Consequently, the molar concentration of
Ag+ and Cl- will also be.t each. Substitutiogin the \o for egcl
= IAs+l [Cl-l
oxpression for solubility product ofAgCl
=rx0 01 = 0'01s
rqP = [As+l [cl-] .. 0'01s = 1'5 x 10-ro
= sxs= s2 or i=l5x10-tM
Btrt \p = 1.2 x 10-to (Giten) , ' \ !! i
Whol is tl& minimunt volunrc of
'1
wdter reEtired to dissolve I g o[calcium sulphatc ot
'" * = 12x10-ro 298K. For calciunt sulphate, Krp = 9' I x l0-o.
y'l r; 10-rt
or r= (N.C.E.R.r.)
Solution.
= l 1x l0-jmolL-l (s) +
. IIXAI\IPII, 2. Lead. cltloide has a solubility
CaSOa <J Ca2+ (aq) SOf,- (aq)
pto(htct of 1.7 x l}-s 298 K. Calculate its If s is the solubility of CaSO, in moles L-t,
:ohtbilily ol tltis temperatltre. thbn
Solution. The solubility equilibrium for x lsol-l =r'?
PbC irepresented as: 4r= 1ca'?+l
"RAe?
calculate the solu bility of silver chloride ir
if the solubility
room temperature
waterat
producr or
4.5 x lo-ze respccrivel),. Also calculillc
molarltles orttiir in,tivldual ioos.
rhc
Agclis16x10-10
[,\ns sohrbility ofAg2cron = 6.5 r 1,,-sn,
L-ll
[.\]rs l'26xlo-5mol
MolarityofAg+=1.30xr0*4M
If solu bility product for CaF2 is 1.7 x 10-10at298
Motarity;fcr;:_ = e.s x to_sNl
K calculatc the solubility in mol L-1. solubility ofHgrl, = 2 2{ x l0-r0lV
I rn' 35x10-a] Motarity of Hgl+ =2.2{ xl0-r0N,l
How many moles of AgBr (\p = 5 x tri-t:
Molarity of I- = 4.4s x l0_roMl
mol-2 L-2; will rlissolve in 0.01 M NaBr solution? 5. The solu bility ofproduct consra nr\ of AS2croa and
I r'r..5 x l0- mol L-ll AgBr are 1.1x 10-12 and 5.0 x 11-13 rcspcc-
Csl@late the solubilities of siker chromate and R
tively. Calculate thc ratio of n]olirrilics ot rhcir
mercurous iodide in water at 298K Giveo that their sarurated solutions.
EE
W.C,E.R.TI
solubility products are l.1x 10-12 and I.\i\.9.151
AR
R
C
FO D IF F IC U LT PRO E} L E I.",{
S
N
!;Wf,trf,,#:0,,,,1|)urf,.,,oy j,nl,";i,!!ri,l!;,;,',;,,r,;r;,,;;;
(ii1 Equul rohunes of 2 x t\-E Al Bd(
Thus, having a of solubility
knowledgc lt.,t,hr.
prod uct o[ any sparingly soluble salt, we can predict tionond 2 x l0-3 lt Naz so1.\oltttiou
,tr( /4ir,tl:,
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8146
Solution. (i) BaCl, ionizes complotely in thc volunrcs, there is no precipitatiott of -iron sulphide ?
solution as
For iron n phide, K", = 3'l x lO-18. 11,1.g.e.n.f)
BaCl' Ba2+ + 2Cl- Pose the concentration of each
-' ofFe isr mol L-1. Then after mixing
[Ba2+1 = [Baclrl =2x10-3M (Given)
cqual volumes, [FeSOa] = tNarsl = ] rrl
NqSOo ionizes completely in the soluticrn as
FeS
1t x to-101 of BaSoo. Hence a precipitate of ZnS = 1'6 x IT-a ond CdS = 8'0 x t0-?.
C
(il) Here, the concentrations bcfore mixing Precipitation will take place in the
IA
are :
solut hich ionic product is greater than
IIT
.. Concentrations after mixing equal volumcs ls,-l = 1.0 x lo-le x 13 = 6 oz,. lo-',
will bc -, = 2' x^ :"
l0-8
= l0-8 M
lBaz+ | lFe2+l = [Mn2+l = Iz*+l = [Cd2+]
2 x to-3 =fxoo+=l'33x'10-2M
and [Sol-l = = 10-3 M
.. Ionic product ofBaSO4 =[Baz+] [SO?-l .. Ionic product for each of these will be
?,B,O,gy,EM,B,,F_O.R
l. Predict whether a precipitato will be formed or Dot 4. PbCt has a solubility product of 1.7 x lO-8.Witl
on mixing 20 ml of 0.001 N NaCl soluiion with 80 a precipitate of PbCt form, when 0.010 mole of
nrl of 0.01 N AgNO3 solution. Itp for AgCl
lead [litrate aod 0.0'10 mole of porassium
= 1.5 x l0-lo [_ L tyill be forEed] chloride are mixed aDd water added upto
2. ll 20 ml oI2 x l0-r tion is mixed wirh I litre ?
20 nrl of 1 x 10-5 M NE SO4 solution, willa ppt. I .lns.yesl
rorm ? (\.p. Ibr Baso4 is l.o x t0-101 ; '.Nol 5. Fquat votume s of 0.002 M solulions of sor.iruur
J. Ca" ions is added to a lilre o .0l M
0.03 nrolc of iorjareandcopperchlorateilrentixedlogclhcr.
SO?- solurion. Will it cause precipiration ot Will it lead to precipitatioo ofcopper iriiate ?
Molarity of AgN03 solution in the final solurioD 5.2NaIO3 + CuCrOo..- NECTOa + Cu(IO3)2
IA
IIT
j(i) In explaining salting out or precipitation stirring with sodium chloride. The process is calletl
oflsoluble sal(s. For example, on passing ,salting out,.
hydrochloric acid gas tfuough a saturated solution
of sodium chloride, the concentration of chloride
ions will be increased. This increases the ionic
product of NaCl and the solid salt will be
precipitated.
_ Similarly, soap (which is sodium salt ofhigher
fatty acids)is precipitated out from its solution by
solutions, tJre concentration of ions are disturbed
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Ne4l
and in place of K"r, we use the sl,rnbol Qr, fiust as the ca-
are not
we use O.in ptacc oIK"). The concept is applicable
se their
even to soluble salts like NaCl exccpt that we use
activities in place of molar concentratious (due to
(ii) Prccipitation of the hydroxides of group
bigh concentration of their ions). Thus in case of
Na('1.
NaCl(s) sr Na+ (rg) + Cl- (0q)
K,, = [Na+ (oq)l lcl- (oq)l
It tlCl gas is passed through the saturated flightly ionised, whereas NHoCl, being a strong
solution oI NaCl, Cl- ion concentration will in- hectrotye, ionizes almost completely to give a
cl cirslj so that Q,, > Krr, In order that Ory may large concentration of NHn+ ions.
bccoure equal to K,r, cquilibrium will shift in the
NH4 OH s- NH1+ + OH-
backwarcl direction i.e. pure solid NaCl rvill
precipitatc orlt. NHoCt NH4+ + Cl-
(.1) ln Qualitative Analysis. The separation D\e lo
-.... ion elecl,
to ahe common aon the qcgrgg
effect, tno of
degree or
ancl iclcntilication ofvarious basic radicals into dil dissociatiou of NH.C)H gets suppressed and hence
Icrcnt groups is hased upon th(r concentration of OH- ions in solution
(u) Soiubility ptoduct ptittciple, according to decreases appreciably. But even with thislow conc.
rvhich 'a prccipitate is formcd if ionic prodlrct is o[ OH- ions, the ionic products of the cations of
gr eatcr than the solubility produc('. R
group III and OH- ions excecd the low values of
EE
(h) Connton ion effccr, according to which'il' the solubilityproducts of their correspondingmetal
AR
to thc sohrtion oI a rveak electrol)tc (like NHoOH), hydroxides. As a result, the cations ofgroup III get
C
r strong clcctrol)'tc having a common ion (like precipitated as their insoluble hydroxides.
(ll) is addcd, the ionization o[ the rveak I! Vand
S
clcctroly'tc is further suppressed. Mg which require a large cooc. of OH- ions due
IA
slightly, while HCI being a strong electrolrte is electroll,tes; ionize only slightly as :
valuesof the solubility products of their cor- lsl+l [Cr(X-l = K,, for SrCrOo
responding metal carbonates and thus get
precipitated. (0'1)[Crol-] =3 5 x 10-s
However, under these conditions, Mg salts do
not get precipitated as MgCO, since its solubility R
or [cro]-l - 3'5] -10-5 = 3.5 x 1o-4 M
EE
product is comparatively high and thus requires a
Thus BaCrOo starts precipitating first be-
AR
precipitation of SrCrOo.
The necessity of addingNH.OH arises due to
IA
a large amount of NH.HCOT. Thus the cations of It is sometimes necessary that a solution of
group V will form not onlyinsoluble carbonates but definite pH be prepared and stored. The preserva-
soluble bicarbonates as well. As a result, the tion ofsuch a solutionis even more difficult than its
precipitation will not be complete. In order to con- preparation. If the solution comes in contact with
vert NHaHCCT3 to (NHl)z CO3 , NHIOH is always air, it will absorb carbon dioxide (an acidic au-
added. hydride) and becomes more acidic. If the solution
NH4HCO3 + NH4OH -.--""r (NH4)2 CO3 + H2O is stored in a glass bottle, the alkaline impurities
present in glass may dissolve iato the solution and
(5) In fractional prccipitation. Fractional
may alter its pH.
precipitation is a technique of separating two or
more ions from a solution by adding a suitable
rcactant that precipitates first oneion, then another
and so on. For example, suppose we have a solution
which is 0. 1 M in Baz+ and 0'1 M in Sr2+. When
a concentrated KrCrOn solution is added (o it slow-
Tlpes ot BulIer solutlors. There are two t)?es
outirst. Wlren most of the
ly, Ba2+ ions pre cipitate of buffer solution-s. These are :
Ba2+ ions (almost whole of it) have precipitated
(l) Solutlons of single substances. The solu-
out, Sr2+ ions start precipitating out. The reason
for this may be orplained on the basis of their tion of thc salt of a weak acid and a weak base c.g.
solubility products as follows :
ammonium acetate (CHTCOONH, acts as a
buffer.
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8is0 ;i'! a' Cottsc Chc tu i stt'q
BulTer Action. frrc prow ! of a bufrer sol.ttion lo CHTCOONa .......- CH:COO- + Na+
resist any change in itr.t pH valte evea when smull ...(r,
urutunls o! lhe acid or ,hz base are oddel lo it L\ By'comrnon ion efrect', the ionization of
called 'Buffer action'. H3COOH is further suppressed. Thus in the solu-
The buffer action of different types of buffers D, there are excess of acetate (CHTCOO-) ions
may be orplained as follows :
d a small amount of HrO+ ions.
Bufier Actlon of Ammonlum Ac€tste Solu-
tlon, AmEoEiuE ac€tate like all other salts, is al- When a few drops of an acid are added to the
Eost completely dissociated in the aqueous above mixture solution, the H3C)+ ions given by the
solution as follows : apid combine with the CH3COO- ions to form
CH3COONH4 , CH3COO- + NH4+ eakly ionized molecules of CHTCOOH.
Thus in the solution there is excess of
CH3COO- ions and NH.+ ions. R
EE
Thus the HrO+ ion concentration and hence
Whcn a few drops of an acid (say HCI) are
AR
by the acid combfue with the CHTCOO- ions to added, the OH- ions given by the base combine
S
Thus the H3O+ ion concentration ofthe solu- H.o+ + OH- 2H2O
tion does not change practically and hence the pH lFro (r)l IGivcn bY the bascl
-
of the solution remains alrnost constant. Similarly, As the HrO+ ions are consumed, the equi-
when a few drops of a base (say NaOH) are added llbriurn (i) shifts towards right (according to Le
to the above solution, the OH- ions given by the Chatelier's principle). Thus more of CHTCOOH
ba*se combine with the NH.+ ions to form weakly dissociates to make up the loss of HrC)+ ions.
ionized molecules of NH4OH. Hence the H3O+ ion concontration or the pH of
NHf, + OH- NH4OH thc solution does not change.
--- Buller Action of Basic BuIIer: The buffer ac-
Thus the OH- ion conccntration aud hence
the HrO+ ion concentration or the pH ofthe solu- tion of a basic buffer e.g NH.OH * NH.CI may
tion remains alrnost consant. he explained as follows :
On thc contrary, the solution of a substance NHoOH dissociates to a small extent whereas
like NaCl cannot act as a buffer because NaCl NH.CI dissociates completely in the aqueous solu-
dissociates completely to give Na+ and Cl- ions. tion as follows :
These may combine with the base or the acid added
to forrnNaOH or HCl. But these ionize comple tely
NH4OH a----\ NH4+ + oH- ...(r)
to give back the OH- ions or HrO+ ions. Thus the NH4CI NH4+ + Cl- ...(r'r)
HrO+ ions crnc€ntration of the solution changes By common ion effect, the ionization of
and hence the pH of the solution changes. NHa OH is further suppressed. Thus in the solu-
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EQUTLTBRTUM 0ONIC EQUtLTBRtUM rN SOLUTTONS) 8/51
-
tion, there are excess of NHi ions and a small But [A-l = [BA], therefore
amount of OH- ions, lHAl
When a few drops of a base are added, Lhe lH3o+l =
K"
ffi: rq lAcidl
lsrl,l
OH- ions given by it immediately combine with . (,,)
NH{+ iols to form the weakly ionized NH4OH.
.. pH = - tog [HrO+l ...(n:r)
NH4+ + OH- .+ NH{ OH
Thus the HrO+ ion concentration or the pH
oI the solution remains unaffected.
= _ rog{ro
#itt lAcidl
Similarly, when a small amount of an acid is =- loS I( - tog
added, the HrO+ ions given by it combine with the [Suttl
OH- ions already produced by NH.OH in equi-
or ...(rv)
librium (i).
Hro* + OH- --, ?H2O or substituting the value of [HrO+] from eqn.
Icivcn acidl [Giv bY (i)l
by thc (i) in eqo. (ni), we get
As the OH- ioos are consumed, the equi-
librium (i) shifts itr the forward direction. Thus pH=-logxr-bclH
more of NH.OH dissociates to produce more of
OH- ions which makes up the loss of OH- ions. or pH=p\+rog$J
Hence the OH- ion concentratiotr and therefore,
the HrO+ ion concentration or the pH ofthe solu-
tion rcmains fairly constant.
EE
-lr::r".*t@..r,
R
Note. (i) From titration curves given in Fig. It is iateresting to observe that if [Salrl/[Acid]
AR
8.3, it may be seen that some portions of the titra- : pH = plq + 1 and if [Acidl/[Sal{ = 10, pH
10,
C
tion curves are flat. i.e. the pH of the titration = p( - 1. Thus if the ratio of the conjugate acid-
S
pH =pK, + logffi
Similarly, for a basic buffer
R
?RACTICE
EE
AR
1 How muchvolume ofo 1 M HAc sbould b€ added monium chloride to give a buffer solu tion ofpH 10.
to 50 mL of 0 2 M NaAc solutioD if wc waDt to civen pK! for NHaOH is 4.75. [,\r,,,. ll2.SIDLI
C
3. is
for acetic acid is 4 76. [rrns. 70 92 nll
N
2, Ho,x much of0.3 M aornronium hydroxide should and iormic acid in a buffer of pH 4.25. [.rns.3.24t
IIT
o,rosffi=o ts
or rogffi= - o.1s =T.2s
1s=1
o, ffi=0.177s
", fir4$=Antiloso
Moles of Salt
41
.
re. Moles of salt
u.l //d
M6tes;IAcid- = l 4l
M6E6TT- =
0.2
o.2
lTfri x )u o.o * g':l =01778 orv=rr2.5mr
r.e -or--= = r'4r ot o.mTtlv = I 4l v
mm'u mr''
3. pK.= - log(1 8xt0-1)=3.74
or V = 100.u 1 41
= 70 92 mL, Iogffi=pU - pK!= 4 2s -3.74 =0.s1.
2.pOH=14-pH=14-10=4
or lsalt]/[Acid] = Artilos 0.s1 = 3.24.
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8154 I Newr Course
t pH of a buffer solution does not change on dilution or on keeping for long time or on adding small amounts
ofan acid or a base.
: pH of a buffer changes with temperature because K* changes.pH decreases with increase of tenrperature.
, Buffer solutions can also be obtained by mixing an acid salt and a normal salt of a polybasic acid e.g.
NarHPOo + NarPOo.
How does the degree ofionization ofa weak electrolyte vary with concentration ? Give exnct relationship.
What is this law called ?
Ans a : '/KV-C. It is calted Ostwald's dilution law (K, is ionization constant and C is nrolar concentration of the
electrolyte).
: Classify ench of the following substances into nn ncid or bnse or both and mention the concepVconcepts
on the hasis ofwhich you can do so.
(i) Hcl (aq) (ir) NH3 (iii) Na,G) co3@O
(ir,) CHTCooII (as)
R
EE
(y) Co, (g) (ri) BF3 (rir') Ag+ (r,iii) cN-
AR
Ans. (i) HCI (aq) Acid (Arrhenius conc.ept and Bronsted Lowry concept)
- -
S
Q. 4 ecles:
IrNO2' cN-' HCIO4' F-' OH-' C()3-' 52- (N.C.E.R.T)
,t-
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EQUTLTBRTUM (tONtC EQUTLTBRTUTV rN SOLUTTONS) 8/5s
-
Ans. NO! , HCN , ClOa , HF, H2O , HCO3- , HS-.
Q. 5. Which of the following nre Lelvis acids ? tI2O , BF3 , H+ , NH.+. W.C.E.R.T:)
Ans. BF3, H+ and NHf (Remenrber that all catioos are Lewis acids).
Q.6 Classify the following into l,ewis acids and [,ewis bases, oll- , F- , It+ , BCl3.
Ans. OH- and F- are Levr'is bases bccause thcy can dooate a pair oI electroDs while H + and BCb are Lewis acids
because they can acc€pt a lone pair of electrons (lo BCl3, B is electron delicient).
Q.7. lvhich cohcept c6n justify that CaO + SO3 ........- CaSOa is an [cid-lrase reactlon ?
Ans. Lewis concept.
Q. r{. Ionization constants Ko for formic acid trnd acetic acid flrc 17.7 x '10-5 and I 77 x 10-5. Whlch acid ls
stronger flnd how many times the other if equimolar concentrations ofthe two are trkcn ?
Ans, Ko for HCOOH > K. for CH3COOH. HeDce forDic acld is stronger.
Kltcoott
Further
Strenlth of HCOOH
Strength of CH3COoH
--.:: = y'IU = 3.16 rimcs.
Kcttacoou
(J.9. Fill in the blanke:
A strong acid has a wealc..,....and a weak base has a strong........
Ans. Conjugate base, conjugale acid.
Q.llr. Out of CH3COO- and OH- which is stronger base flnd why ?
Ans, OH- ions can combine with H+ ions nore rea<jily rhan CH3COO- ions can do. Hence OH- is a srollger
R
EE
base.
(1. ll What will be thepH ofl M N0NO3 solution at 25'C ?
AR
Ars. NaNO3 is a salt ofstrong acid and strong base. Ilencc its solurion will be neutral. At 25'C, irspH will be = 7.
C
Q. I
N
A"".
" = fi;/ C= z M where M = nrolariry
IA
Q. 13. What is the elfect of temperature oD ionic product of water and why ?
-Ko
IIT
Ahs. Ionic product of watcr (Iqd) increases with increase of temprature because Iq = [H3O+] [OH-] aDd
dissociatioo of FIzO to Eivc lt3O+ and OI"I- increases with increase of tempemture-
Q. l.l What happens to the idnic product ofwrter i[some acid is added into ttrEter ?
Ans'
P\e = - los K,, = - log 1o 1a= 14
Q. l6. Whflt are pH ond pOH vnhes o[ a neutral solution flt r temp.rrt[re at which K, = 16-rJ i
Ans. pKl" = pH + pOH- But/Iq = 13. Also, for neutralsolution,pH =pOH. Hence pH = pOH = 6.5.
Q. 17. The ionization constants of IIF is 6.E x 10-'. Calculrt. the ionizatlon consttrnt of the corrcspondllg
conjugate hose. (N.C.E.R.T)
Ans. Kb=Kr,/q= rc-14/(6.8x 10-a; = 1.47 x t0-rl :1 5 x l0-1r
(l -.:! Through n solution contnining Cu2+ nnd Ni2+, [IrS gasispnssed after adding dil HCl, which lvill precipltote
C
Ans, Cu2+ will precipiiate out because in thc acidic medium, only ior:ic proriuct ICuz+ I [S2- ] exceeds the solubility
N
product of CuS.
IA
r., tii why in Group V of qualitative nnnlysis, sullicient NlloOH solutioa should be added hefore adding
IIT
(NH.)2CO3 solution ?
Ans. This is done to convert NHaHCO3 usually present in Iargc amounts alontr ith (NHr2CO3 to (NH1)2CO3
NHlHCO3+NI14OH+ (N IIa)2CO3 + H2O
(2 17. Whnt is pll of our hlood ? lvhy does it remnin dlmost constflrrt inspite the yariety of foods oltd sPices
e 10. Benzoicocidisamonobnsicocid,When122gofitspuresampleoredissolvedinwaterandtitratedagainst
base,50mlofo 2 (N.C.E.R.T)
M NaOII are uscd Up. Cfllculate the molst mnss of benzoic acid.
Ans. 1000 nrlof t M NaoH will neurralize acid = ij# " 1ooo = t22 s
But 1000 ml of 1 M NaOH contarrr 1 mole of NaOll and will neutralize I nrole of mooobasic acid. Hence
nrolar mass ofbenzoic acicl = t22I mol-1.
(J. -t I A solutioh gives yellow colourryith methyl orange, methyl redcnd phenbl red. What is thcPHof the
solution ?
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EQUTLTBHtUM (tONlC EQUtLtBRtUM tN SOLUTTONS)
- 8ls7
Ans, Yellow colour with Dethylorange meanspH > 4.5
Yellow colour with methyl red meanspH > 6.2
Yellow colourwith pbenol rcd meanspH < 6.4. Henc€ the lolution haspH bchpEe n 6.Lao 6.4.
Q.32,ThelonlzstloncolsirDtoflormlcacldlsItxl0-'.Arou[dwhatpEl" lltsmtlturrtrlthlodlumforIlstr
give huffer solution olhlShest capacity ?
Ans. Buffer solution of highcst capacity is formed at whicbpH - plq - _ log (f .8 x l0-l _ 3.74.
CARRYING ,I MARK
Q'1'whotlsthelsvcall.dwhlch8lv€rchdoDsblpbctrccrd.grGcofdlmtodo!ofrr..kclet,lyt.Ddlt
concentratloD in thc solution ?
Ars, Ostwald's dilurion law.
Q. 2. Whot ls the dillerence b€tnccD a coqlugqt ocld ard o coEJugsaG borc ?
tus A coniugate acid and base differ by a proton (Conjugalc acid q=* ConjugaE bolc + H+)
Q. 3. Wtitc the cxPressioD for comParison of relative strengths of two mat acids in tcrlllr of thalr ionizrtlon
coDsialrts.
*-ff*!{ffi =\€
Q. 4. Whnt is the flctive mass ofwater ?
Ans. 55.5 mol L-l
R
Q. 5. How can we predict whether a precipitate wlll be forDcd or not on mixing two Golutiotrs ?
EE
Ans. A precipitate will be formed if ionic product > solubility product
AR
Q. 6. Whnt happels when HCI gos is passed through saturated NaCl solution ?
C
Q. 7, Whnt is the
N
Q, tl. Whar hrpl,ens to the ptl if ! few drops of rcid are added ro CII3COONHa solutlo! ?
Ans. pll will rentain
almost comtant (beinga butfer solurion).
Q.9 which ihdicotor shourd preferably be used for titration ofNHaoH with Hcr sorutton ?
Ans. MethyloraDge.
Q. 10. Whot is the relationship betweenpKh aDdpH ot thc equivalence poilt ?
turs, /,I!n = pH ar the equivalence point.
Q' 1l' At half-neutrolisation ofn weok acid with o strong bflse, what ls the relfltloNhlp betwc.rplf ord dlssockrtlor
constont (q) of the rryesk ocld ?
Ans. Al halt-neulralisation.pH - pKs,
Q. 12. lvhnt is the rrnge ofarH indicator in terms ofits dissoclodon constrnt (Kh) ?
Ans. pH =pK,n t 1.
Q. 13. Whrt hflppens to the solubility ofAgCl in nater lfNnCl solutlon ls added to lt ?
Ans. Solubrlity ofAgCl decreases due to common ion effect.
Q I4' *'rnt is thc rerationship between pl(o and pKo varues nhere Kn and Ka repr€s.nt ionrzaron constaDb or
the scid nrd its corJugote hase reslectively ?
Ans. pq + /rK, = pK* = A.
Q. 15. lryhat is the relationship hetryeen pH {nd pOII ?
Ans. pH + pOH = pl<w 14. -
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8/s8
,) r.t.i('t'i,'s Neqt Course Ch.mistrq@
CARRYING2oT3MARKS
the deSree of
Sec.lt.l. l. What are strong and weak electrolytes ? Derive ao expression for the calculation of
ro lt..:. ionization ofa weak electrolYte.
2. Derive and defioe Ostwald's Dilution l-aw'
Scc. tt.-1. 3. DeIiDe tho follo\.t'ing giving €xamples :
(i) Bronsted-Loery acid (ri) Bronsted-Lowry base (iii) Conjugate acid (iv) CoDjugale base
(v) Lewis acid (vi) lrrvis base
Disqrss lhe Proton tramfer theory (Bronsted Lo\T thcory) of acids
8nd bases'
4.
5. What is meanl q the conjugatc acid'base pair ?
the Bronsied definition ?
6. Discus Lewis delinition ofacids aDd bases. How is it more useful tban
Deline the tcrms 'acid' and 'base' ac.cording to each ofthe follo 'ing conceP$
:
to 8.5 "rpf"in
or ionization consunts'
10, Discuss the strengths of acids and bases in terms of their diss@iation
ba'sc and strong base has a weak
ll. Justiry the slatement that a strong acid has a weak conjugaie
Scc. t.6 12, the ions of weak or sttong acid or base are allowed to iDteract with water ?
useful in
Src.ll.7. il: tand by the term'ionic Pr-oduct ofwater'? Hqw has this concept beeD
R
EE
to t.li. nd basicity ofa solution I
4, ExplaiD the term 'ionic Product of w'ter'
AR
'l
rs. whaido iou undersrand by ,pH sc2le, ? cao a solul ion have pH tess rhan 0 or more than l4 Explain
IIT
Sec. t.12. 22. Brietly explain why PheDophthalein is oot suitable indicator wheo the base is weak acrd why methyl
a
25. Why most of the indicators have a useful colour change over a PH range of 2 units ? Prove
mathematicallY.
result
26. Hou, is pK of a weak acid or a weak base determined from the titration curve ? Derive the
matbenlaticallY.
equation' ryM1Y = n.-M2Y'
2?. Derive norrnality equation, NrVr = N2v2 and the nolarity '
acidity and basicity of the base and the acid resPectively'
where n
I and n2 arc the
2ll. ExPlain thc terms
ion elfect
1ij solutritity proouct (ii) Common
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EOutLlBRtuM [ (oNtc EoutLtBHtuM tN soLUT|ONS)
- 8/s9
29. How.does solubility producl differ fro, iooic product ? Discuss two important applications of
solubility product
30. Give rcasoDs for the following :
(i) zDc sulPhide is PreciPirated by hydrogen sulphide ftom an amD.loniacal $olution but not fiom
stroDg hydrochloric acjd solutioo. ir
What are the advaDtages aod limitations of this co[ccpt c,ver the
.
S
earlicr mncepts ?
Sec. {.l,4. 4. Derive_ expression relariDg the stleDgrhs of m )nob;t u"ior'li.or"
N
Sec. E.7. 6. txplain the tcr,,, ,lonic producr of \rhter, and ,pH'vatue,, How
does the former cba[ge with
lo ti.9. temperaturc ? Whal is pH sc{lc ?
Scc tt.l0. 7. Briefly explain the tcrDs-Sall ll1dro[sis, hydrobfsis constant and
degree ot hldrolysis. Derivc
t0 E.l l. opressions for thc calculation otpH of' '
(a) salt ofstroog acid with crat base (r) satt ofweak acid
with weak base-
Scc,lt.l2, t. D6cribc Ostwald,s theory of Acid-Bsse illdicators.
9. Brprain the diff€rena types of acid-base tirration curves.
How is a suitabrc indicator serecled for a
particular tirration ?
Sec.8.lJ. 10. B-riefly cxplain the term ,solubility produrl., Disc.uss its aDDhcarion
to 8.15. (r) ill calc.tllatio ofsolubility ofa sparingty solubtc salt (ri1 in quatitative anarysir.
11. Frplain 'Common Ion Effe{t,.
Stc. li.l 6. 12. What ir a 'Bufier solution, ? What are difierc[t types of buffers
? Dhcuss their buffcr actio[. Wbat
k the importaocc of buffers iD biological prcess;'?
Derive expressions for thc pH of (a) aD acidic buffer mixture (D) a basic buffJr ntixture
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2.,
ONiALSI E
solvents' As already explained' acids like HCI' HNO3'
1. tevelling elfect of water and dilferentiatiDg
in water dissociate alnosi completely r"e
their dissociation equilibrium is almost
H2SO4 etc. wtrci ttissolved
H3O+ + Cl- or may be uritten simply as HCI +
H'O --
completely to the right (e.& HCI + H2O <-
all acids stronger than
I{rO+ + Cl-). These acids behave a's equally stroDg in water' In fact' in aqueous solutioD'
R
EE
AR
C
S
N
IA
(4{)
p.g. Haoa (uD+ cH3cooH (d4) <----\ clo4- ('9) + cH3cooHz+
I{No3 (.!q) + cH3cooH (aq) + Not ('I4) + cH3cooHf (44)l
.rheireorrilibriumconstantscanbedeternrinedaodhenc€theirrelativestrengthcanbefound.ForexanPle'
ti und to be in the order
," *J;;,h"1*.-h';;;rion.i uu*", tt'" 't'"ngths are
HCIOI > H2SO4 > III > HBr > HCI > HNO3
completely'
strong acids and strong bases dissociate almost
Lastly, it may be mentioned lhat in water' as
K, or KD has no meanlng.
Another solution'
2. on change ln PII on dilution or mixlng i{ith
Ar lnterestlng ol'serYatlon
volttme becomes double' the pH of the diluted rclution
If o solution of PH = 2 b dihued with woter so that the
: PH = 2 nreans [H3o*] =
t0-2 M
can be calcululed ar follows
r
r'r = 5 x l0-3 M
After dilution to double the volume, [H3o*, = 5'
PH = - log(5 x 10-3) = 3 - log5 = 3 - 0 69e - 2 3
r/60
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EQUTLtBRtUM 0oNlc EQUtLtBRIUM
- tN SOLUTTONS)
8/61
ADDITIONAL UgEFUL TNFORMATTON 6ohrd
I NFoRMATToN
ao.lld
-^9SLISNAL U9EFUL
BiOCI from Bi(oH)zCl bY loss of H2O'
ll$m h oxYEhloride
-Ite solubility ofa salt of weak acid i[creases if the solutioo i6 made more acidic
Effect ofPH on solubility,
5.
pH n- a""i""JJl ioi exurnir", ctre sorubility equilibrium of CaF2 Dmy be repres€oted as
<ir.
CaFz (1) -: t:az+ qaql+zr- 1oq1
I{+ ions wil! combiDe with the F- ioDs As a result' equilibrium will
oo makiogthe solution more acidic,
shifl forward i.e. solubility will increase'
coDcept b€causc it can ciooale a lone pair of (iv) A brovn PreciPit8te iD o bottle cotrtaining
aqueous FeCl, solution aPPcars on standing'
C
electrons-
.) 1 Glycine is ar a-amino scial which exists in the iorization ofNH4OH
S
form of Zwitt€r iotr as NII3CH2COo- ' Write due to common ion effect. Hence concEfltration
IA
(., ,' -
- Brown ppt. (sr) NHt , NH4+
Why Po3 ion is rot arnphiprotic ?
(iv) s2-, H2s.
18.I.T Ratchi, t990)
Ans. Ar1 rmphiprotic ion is one which can donaLe r.' I NaCl solution is added to s saturated solution
ofPbCIz, rffhat will happeD to the concertration
protoo as well as acccpr proton. poi- ion can
accept proton(s) but cannot donate any proton. ofPb2t ioas ?
Ans. Pt2+ ion concentration will
Hcnce POi- is Dor amphiprotic. decrease to kecp
!, - In the reaction hetweeh BF3 and CrHrOCrH5
\, constant.
,.
v ',,- Mich is astrongerbase in each olthefollowing
which oDe of ahem will act a6 an ccid ? Justiry
pairs and why ?
your ansver. (I.S.M, Dhanbad 1990)
Ans. The reactioD ber\reen BF3 aDd qH5OqHj is
(i) H2O , Ct -
(ii) cH3coo-, oH-
QHs.. i
qn,io'* f -t (D Hzo
F 0i) oH-.
Refer to Bronsred-Lowry concept for retattve
strengths
QHr\ .._ Bi F th R
EE
-o
9H,- -
i s,h
AR
As Blj
accepts a pair ofelectrons, herice BF3 is s
C
rhus
",=3t:;=
g (0
I'rohleDt
cortsining
2. CaLld.lit the ratlo of pH ofa solution
I mole ofCHTCOONa + I Eole ofHCl per
./!so IH+l = Ca litre to that of o solutiol contoirirg 1 mole of
0i) CH3COONa + I mole of CH3COOH per litre.
Substiruting rhc value of C from eqn. (i), we gct
K rl -ar K.(1 -a) . Case l. Calculation of pH of solution
[H+] = -ij-z---: or a-- containingl mole of CHTCOONL+ I molz oIHCI per litre
CH3COONa + HCI
,.* ,, *, = - ,a, O + rog 1r -
CH3COOH + NaCt
- "y"-
rog,l -
lnitial l mole lmole 0 0
or pH =pL - log(l - a) + loga
moles
1_- Moles00l1
or log :;-: = pKo - pH
after reactiorl
or li'=tctr"-N r.e. [CHTCOOH] - I mol L-r
or ]- I = rrr*"-rH CH:COOH ;S CH3COO- + H+
lll3o+l = r'qT'
.'. [H+l -c@Bu!d "tr
R'' lH+l =.8
-*==y1.-=K1/2
EE
(c.B.s.E. PM.T 2004)
Ans. Refer to page 8/30.
( C= lmol t-l;
AR
!l roIlsted
i.e. K,
N
(i) Whzn I l4lh of the acid hlu been neu,l't lized .. o'1vx 1 -3.oxro-3
CHTCOOH + NaOH- CH:COONa + H2o 136 V'
or V'- olV -=0245v
lnitial 0 1M
136x3x10-r
conc. . . Volune ofwater evaPorated
0.1x
?l 0lxi =V -V,=V -o.Z45v = 0.755 V
Afrer l/4rh i Le. ofwater should be evaporated off.
75 57o
neutra- 5
A butfer solution with pH 9 is to be
)'rohltn
lization = 0.075 M 0.025 M prepared by mixing NH{Cl ond NHaOH. Colculote the
numher ofmoles ofNHaCl thatshould he addcd to one
.. PH =PK, + ros##+
litreofl 0MNH.OH (Iq=I E x 10-s)
=_togl0-.- + logo:d6
0.025
(M.L.N.R. AIl4l abad I99I )
PKa = Kt
Afrer 3/4th o.t x f Ivf o.r x Irvr -log
= -log (l 8 x rc-\ = 4'744'1
ncutralization
=0.025M =0075M [Base] = [NH.OII] = I nrolL-l
'. R
EE
,. pH = - loc lo-5 + Ios &3# 5=a7aa7+losEq
AR
Prohlen 1. A saEple of hnrd water contoins 100 t'rohlrm ('. c.alculslte the amounl. of (N IIa)2SOa in
ppm ofCaSOl,What Elinimum fraction ofwnter should
S
(M.L.N.R tee2)
MaxiDum solubility of CaSO4 irl water Solution. As it is a basic buffer,
can be calculated from its Krp value as f'ollows :
pol=pK6+ l.c1$#l
S='.q =V9Oxl0-o IN H4+ l
=3ox1o-3molL-1. = - ros KD + loc
I-NHFEI
SuPPose the volume ofwater taken = V litre
,ds pH =9.35, .. pOH = 14 - 9 35 = 4 65
As CaSOl present is 100 ppn rle. 1008per 1068 of Milli moles of NHaOH in solution
water, therefore, CaSO4 present in V litres (V x lo38) = 0.2 x 500 = 100
ofwater suppose milli moles of NHn+ to be added = x
= **
10" "
v x rrPg = 6.; vs = !{}motes . 4 65 = - log(1 78 x 10-5; +.r#i%
(Molar mass of CaSO4 = 13r,8 nrol-l ) = (5 - 0.250a) + logiloo
V'litre
After evaporation, suppose volume o[water left = or tog
1fu = -0
0996 =i oooa - o'r
or logx=2l or x=125 9
ThusV o[waterwillnow contain n:oles '. Milli moles of (NH4)2SO4 to be added
lrtre !f
125 9
of CaS04. = ---'- = u''"'
This should be equal to the ma\inlum solubility ilr
moles L-1.
( 1 nlilliDrolc of (NHa)2SO?=2 millimoles of NHf)
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EQUTLTBBtUM
- I 0ONrC EOUtLtBRtUM tN SOLUTTONS) al67
. . Mass of (NH{)2SO4 ro be added
Kp for AgBr = 1ag+1 1rr-1
= (62.sS t r O -3 moles) (132 t mot-l) =@+ y= 5.0x10-13 (clven) ...(i,
= 8.i094 g. Dividing 01) by (i),
I'n*lin 7 Givcrl that the solubility product of
radium sulphate (Rosoa) is 4 x 10-lI. Cslculate the I=u, or | = O 5x
solubility in (a) pure wster (r) 0.10 M Na2SOa. Putting in (i),
(I.SJU Dhofiul 1992) (r + 0.5.r).r = l0-12 or l.5l = 10-12
ot l-9.667r1q-tz
(a) Suppose the solubility of RaSOI in
or x = 0 82 x 10-6 mol L-l
water = -r mol L-l.Tbeo
.. y- Q.J;=o 4l x10-6mot L-l
Raso4-Ra2++sol-
imolL-1 Solubility of ABSCN = 0 62 x t0-6 mot L-r
r mol L-l r mol L-l
Solubility of AgBr = 0,4t x 10-6molL-l M
\, = 1na2+1 lsol-; l'rohlotr 9. Colculate the hydrolysis constant of
= rxx= ? the salt cont$ining NOr- ions (Given q for
or l= 4Y 16-11 HNO2=45x10-lo (M.L.N.R. 1996)
or x= 6.66 x,l0-6 mol L-r For the salt containing NO; ion G.a salt
(D) NEso4 .._ 2Na+ + sol- ofweak acid)
As INE So4] = 0 10 M, R
-, K- lo -4
Kr=d=*i.=-u-2zyto-s.
EE
.. ISo;-l from NE so+ = 0.10 M
AR
SolutioD. l, - R;7
IIT
pl=pY\+.c a=3 8+
At?'C, pH = 7 means [H+] = 10-7 M R ffi" loc
ffiS
EE
.. *", = 10-to
or or
ffi: 1 584e
AR
ros
At 35'C,pH = 6 n:eans [H+1 = 10-5 M ffi=o.z
C
= 10-12
Krr, o, ffi$ffiffi=r'ssre
S
HzO are in thc same ratio as ionic Products ofwater, wc ( . Volume is same for both)
IA
1.fl) x 10-? ond 1'30 x l0-rt rtspocttvely st 2yc. /'ri,li|ra J Colculate the PH at equivolence Point
when a solution of 0 10 M acetic acid is titrated with o
(Roorkee l9EQ
solution of 0.10 M NnOH solutlo!. Kr for ocetic acid
I! << \. Hence H+ ions are maiDly
-qg!CE-o!. = l.9xlo ' (Roorkee 1990)
from lst dissociation H2S <-----\ . At the equivale[t point, CH3COONa is
-- tH+l IHS-I formed and its conceotration = !_l M = 0.05 M.
' IHusl
It is a salt ofweakacidand stroDg base. The formula
or rr+1 = {, grpl for finding the pH of such a salt is
... [H*] = 40-\ 10" = 10-a pH --+ IlosKq,+ loglq-logcl
Hence pII = 4
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EOUtLTBBTUM
- 0ONrC EQUtLtBRtUM tN SOLUTTONS) 8/69
or Lac- + H2O R
Case Il. Afler adding 20.0 mL of 0.1N HCt,
EE
OH- + HLac pH = 9.14
=- ..pOH=10-9.14=486
AR
Hyd10l)6is constant,
=
'. =- "'(o nrilli moles
S
'c'
-Fi'-molL-l BOH + HCI _ BCt + Hzo
N
But
IA
afier reaction
lo8 [OH-] = 5 60
- a
or .. 4.86 = - tog Kb + log (...x)
[OH-] = sD11qr 1-, ,, r--:--
Subtracting eqn. (i) from cqn. (ii), we get
= 2 51 x l0 -6 M
4 86-3.%=toEi4- rog,#T
Iq= or 0.9=log2-togtr-2)
= 1 21 x l0 " - log 0.5 + Iog (r - 0 ,S)
Further for the weak acid, = 1.105 x 10-3 x ?4g = 0 0818t = 81 8m9
HA # H++e- .. Amouoi of Ca (OH)2 precipitaled
From cqns. (i), (ii) and (rri), Mg2r ions. K, of Mg(OH)2 = 1 x 10-rr.
R
EE
solution. Minimum [OH-l after which
x=ft-ffi=ro"
AR
Ca (OHt .....- Ca2+ + 2OH- tions. What volume of5M NaHCo, solution should be
mixed with a 10 ml sample of l)lood which is 2M in
.r Ksp -- tca2+l toH-F IITCO3 in order to maintain a PH of 7 4 ? q for
= xx(2t)2= 4l HrCOrinbloodisT.t x 10-7. (I.I.T l99i)
. 41 = 4 42x 10-s
or .t' = l.lo5 x lo-5 -sdc@. pH =pK" + rou ffi
3 lo8! = log (1 105 x 1o-5) - [NaHCOll
7'4- - log (7 8 x l0-') + log
ffi
= 0.M34 - 5 =-4.9566
01
logx =- = 2 347A
1'6522
x=2227 x Lo-znolL-r
,"rffffi =7 4+ (-7+o'8Y21)
. . Amount of Ca (OH)2 Present in 500 ml = 1 2921
x lo-z x'l49
=2
- --
Z--
221
or sffi = Antilons 1.2s21= ls ss
K.
H,S As plj = 12,... [H+] = t0-t2
------.: H+ + HS
C
K2
HS- <-
N
.. MolaritY of the solution renction of NHa+ and OH- to form NH3 artd H2O nt
S
N
,=€ =0607x106=60?x105
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EQUTLtBRTUM (ONIC EOUtLtBRtUM tN SOLUTTONS)
- 8173
lrohlut l9 Calculste the pcrcertage of +
hydrolysis ir 0 003 M aqueous solutiol of NaOCN ,, [c6HrNH3]JOH-l
(K" for HOCN = 3.33 x r0-4 M) (Roorkee 1996)
Nr'=-TQENET- ".(4
Solution.NaOCN + H,O €=---r NaOH + IIOCN Further, we arc given
+
or OCN- + HzO + OU- + HOCN c6ll5NH3 cofIrNH, + H+
Initialconc. c -) +l
Conc. at eqm. c ('l-1,) ch ch
,. lc6H5NHrl lH
^.=_-----_i-...(Il)
=C lc6H5NH3I
where h is the degree ofhydrolysis Arso IH+l IOH-I = Kr? ...(r,,
.. Hydrollsis constant, Combining eqns. (i), 0?) and ( )
K, = ch ;ch =r1,2 or h={yj, ,, K* lo-t1 to-8
^,=4=r;;ro-=z.a-
gr1 K. = IOH-l IHOCNI
- IocN-l
SubstitutiDg rhe values in eqn. (i), we get,
10-8 l0-8 xr
K,=rH+l5oeR'r-l tHocN + H++ocN-l i=T =tr which gives r=to-2M
Problen 2l.l sa6ple of hard water contelns 96
K. = tH+l IoH-l ppm ofSO!- ond tt3 ppm of IICOJ- with Ca2+ as the
Combining these equations, onlycntion. How mary moles ofCaO will he required to
,. K,, 10-14 remove HCOt ltom 1000 l(8 otthts wsrer ? If l0O0 kg
^r=x;=a:5:,ro= R
of this water is trested wlth the amount of CaO calcu.
EE
laied above, whet will be the concentrotior (in ppm) of
lo-10
AR
I
T5r'r;lo-3 = {l:r'= 16-o residuat Co2+ ions ? (Assume CACO3 to be cornpletely
C
remoining solutlon cotrtstucd 0 0026 g ot Cl- per lltrc' lsaltl + [Base] =0 6molL-l
CatculatJ the solobtltty prodoct ol fuCl (Kr lor 0 2 mol L-l
This on solviDg gives [Basel =
A82CO3=t z x ro-2; (I.I.T teen 4motl-r
and [Sflltl = 0
1 .5 M Na2co3 gives ICoS-l = l 5 M t'n,l'ltn )5. K, for ascorbic acid (HAsc) is
Ile for As2co3 = lAs+F tco3-l
= (kn*ee 1997)
tco3-1
Solution. As ascorbic acid is a weak acid, aqueous
C
=2'34xlo-6M
solutioD of ,{.sc- meaos the solution ofa salt ofwsakacid
S
giveo by
=(2.34x10-5(#)
,=\T-Vr;im=
IIT
=171 xt0-lo
Pa,httu 21. At acidtlIp lrdl@tor, HIn dilfers lu
= r0-4 = l0-a x tOO% = O.Olqo
colour ftom lta coqjuSstc bose (In-). Tte humon eye is
seEttive to c{lour differ.nces only wher the ratlo Asc- +H2O + HAsc + OH-
lltr-I/tgbl ls 8Ert r thatr 10 or smollcr thsr 0 1'
i{hai shoul! bc ihe mhltEum chanSc ltr the pH of the L-l
c mol
oriz
rn-14 = 0.32 s L-l = mor l-r
or 'lH+l= rv -=5xt0-12
2xl0-' =0 01 M = l0-2M
'. PH=-log[H+l =-tog(S,. I(, for N2H{ = 4.0 x 10-6 M (civco)
ro-12) R
EE
= l2 - 0.69 = 1r.39
10-1.
AR
solution. Kry for AgI olld K. tor Ag(CN)2- are = | " 16-: = n.. x l0-3 = 0.1sq,
S
l 2 x lO-1 M2
N
^nd
(Roorhee I 99E) 6 7 x 10-5 ltl. Calculate the solubility ofpb(OH)2 in a
IIT
,
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8n6 t)rt(.7p.e p's Netl Coutse Chem istrLfiffi
NeglectiDg this cotrc. in eqn. (i), we 8et
rog+ll- - r
lAg(NH3)z+l - o'1.
lsalt] = 0.05 M
For bufier'{ ---9j...._:=r.o*to'
l0-e x [NH3]!
when equalvolumes ofboth the buffers are mixed, [NH3] = 2 5 +O'2=2 7M'
.l'r.)rl€r, -J.i. The averoge concentratlon olSO2 ln
lAcidl = 0 '5'
the atmosphere over o city on a certah day ls 10 Pprn
1sattl =IJ-9-91 =z sozs when the avernge temPeroture ls 29t K. Giver that the
solubtlity of SO, In nater at 29t K is 1'3553 moles
R
EE
pH =p Ka + rosffi,I+ litre-l and thcPKd ofH2SOS ls 1 92' estimste thePH
ofrr|n on that dry.
AR
GI'I2000\
2.5025
=s+rog_otj_ Solution. SO2 + H2O -- HrSO3
C
S
=5+1o85'05=57 litre-l
N
r.e
.
, 10,= ttu(NH3h*l (rr) or log K.d = - 1'g2or'Ka= 10-1
e2)
b= lAf I1NHF
Neglectingrz in comparison to 1 3653, we get
F\rrther [A8+] [cl-l = K"p = 1o-lo y' ,,.,-r.ez
-
2xT:36tJ-'"
or [Ag+] (0 1) = 1o-ro
or
or f =z noe ,1 16-1 92
[A8+l = 1O-e'
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EQUTLTBBtUM (tONtC EOUILtBBtUM tN SOLUTTONS)
- 8n7
or 3 logr = toE2.73O6 - 1.92 A8NO3 left = 0.01---0.005
= 0.005 mot. Whotc
= 0.4348 - 1..92 - - t.4t5Z of it will react completely with N%CrO1 (as it is presenl
or -logr=0.485 in larger amounr).Na2CrO4 reacted
= 0.0052 = 0 OOX
i.e. pH = 0.4t5. mol. Hence NECTO4 teft = 0.1---0.0025 0.0975 mot
=
lrntbk'n .1J. What lIJ,rO +l hust be maintained in
AgzCrOa (ppr.) formed = 0.0025 mot.
n satumted H2S solution to precipltate pb2+ lrut not Total [CrO:-] = 0.0975 mot + CrOl- obrained
Zn2+ from a solution in which each ion is preselrt at a from Ag2CrOa (negtigibte)
concentration of0.01 M ?
IK,? H2S = I .I x 10-22 anrt K, ZnS = I .0 x l0-2rl - 0.0975 mot = 9.7S x l0-2 M
(Rarkte 2000) AgzCrO4 + CrO;-
-2Ag+
Kry for ZnS = to-2r K,p (A82CrO1) = [A8+ j2 ICrOl-]
and [Zn2+1= o.U M - l0-2 M I 1g-2; = 16-8
IAB+]2x(9.75
But KrP (ZnS) = [zn2+] [s-2] or [Ag+]2 = 0.1 x 10-6
i.e. 10_2r = [10_2] [S2_] or [ng+] = 0.32 x 10-3 M
or [S2-] - lo-le M = 3.2 x lo-4 M
Thus to preveni precipitation of Znz+ ions,
lS2-] R
Total precipitate formed = 0.005 + 0.0025
EE
must be less than l0-19 M. Further
= 0.0075 rDol
AR
l.6Xt00 =22x1O-t6
-' =8 x0.t = 0.E
S
N
ot
IA
Eq.wtofNaOH=40
A- +H2O ga+OH
=+ .. 0.4 M eq ofN%Co: =
For sucb a salt, 1ffi x 0.+ = o.o2t\g
pH=7 +
+lpKo+ togcl
0 6MeqofNaoH = ffi , o.c = o.rzr
_(d) 75 nrl
of Gv!s) HCI + 25 ml of (M/5) NaOH
5. At 90"C purewater has [H3O+l = 1o-5 M what
S
t l.l. l. !t)gL:
N
is the value ofKl, at this teDlPeraNre ? 10. Which of thc following will occur ifa 0 1Msolutioo
IA
the lowest value of Ksp at ordinary temPerature 12. The prccipitate of CaF2 (\, = l 7 x 10-10) is
(about 25'C) is oblained when equal volumcs of tho following aro
(4) MS (oHh (b) ca (oHh mixed:
(c) Ba (OH)2 FlBe (oH)z. (4) 10-4 M ca2+ + F-10-4 M
(I.LT l99o M Ca2+ + lo-3 M F-
.llb) to-2
1.c 2.a 3.b 4.d 5.b 6'd 7'd E'd e'd 10' c
11. ,
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EQUILTBBTUM
- I (ONIC EQUtLtBBtUM tN SOLUTTONS) 8/81
(c) 1o-5 M caz+ + 1o-3 M F- moles of HCN in water aDd lDaking upto total
volume to 500 ml is
(d) 10-3 M ca2+ + l0-5 IUF-.
<tq 9.3o (b)'7 30
. (c) 10 30 (l)8.30. it ,
lsfas* (D) H2O 20. Whal is thc percentagc hydrolysis of NaCN in N/80
(c) cN- (d) NH3. slutioD $'hen thc dissociation conslaol for HCN is
I 3 x 10-e and Kx/ = 1.0 x lQ-la
15. Which anion is the weakest base ? @)2.a8 (b)s.26
(,) QHso- (d) Not 2
(.) 8 (d) e.6
t' : | 1 l
(c) F- (d) cH3coo- \
'.?t. Thepll indicators are
(4) ofstrong acids and srrong bases
salts
16. The correct order of increasing [H3O+l in the (D) salts ofweak acids and weak bases
following aqueous solutions ts .. (c)
(.r) 0 01 M HzS < 0.01 M H2 SO4 R eitber weak acids or weak bases
EE
(r/) cither strong acids or strong bases
< 0.01 llt Nact < 0.01 M NaNO2
AR
(6)0 01 MNaCl <00lMNaNO2<0.01 M 22. -Ihe solubilily producr of AgCI is 4.0 x 10-10 ar
C
be
N
H2S<001 M H2SO4
IIT
(D) concentration of Mn2+ .14. The srrondest base of lhe tollowing species is
is Iowercd by the forma-
tion of complex ioDs with chloride tons (a) Nrr2- (6) OH-
(c) concentration of sulphide ions is lowered b_v (.) o. (d) s,-
oxidation to tree sulp-hur
(l) conceDtration ofsulphide ions is lowered by the 25. Which of rhe following sutphides has rhe lowesr
lbrmation of lhe weak H2S. solubility product ?
(4) Fes (b) Mns
It. The pKa of HCN is 9.30- The pH of a solurion
) (c) Pbs (d) ZDS
prepared by nri\ing 2.5 moles of KCN and 2 5
12. b 13. b 14. o 15. b 16. c 17. d 18. a 19. h 20. a 2t. c
22, c 23. c 24. a 25. c
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8182 Net4 Course Chemistrg
26. The pH ofa solution obtained by mixing 50 ml of pfAutoprotolrsis constant of water increases with
0.4 N HCI and 50 mlof 0 2 N NaOH is temperature
(a) (r) 0.2 (d)Wheo a solution of a weak monoprotic acid is
-lo9z
(c) 1.0 (d) 2.o.
-log titrated against a strong base at halfneutraliza-
fion Poioi, PH = (12)PK.a. IIT t992
i,.
The concentration of [H+] and IOH-] of0 1 M
27. lD a mixture of a weak and its sall, lhc ratio o[ thc
aqueous solutron of2oZ ionized weak acid is (ionic
conccntration of acid to salt is incrcased tenJold
'[tepH ot the solulion product ofwater = t x 10-1a.1
(a) decreases by one (r) decreases by one tenth (a)0 02 x l0-3Mand5 x 10-11 M
(c) increases by oDe (d) iDcreases ten-fold. (b) I x 10-3Mand3 x lO-11 M
(c)2 x 10-3M and5 x lo-12 M
2t lfa neutralsolutron hasPKv = 13 36at50"C (heD
(d)3 x 1O-2Mand4 x 10-13 M.
plI of the solution is
(A 6.68 (b)1
The strongest conjugate base is
(c)7.63 (d) None of these
r.4.li,1I (. l\tnt 1997, K ttla l: l: I -""' i (a) Nol (b) cr-
LrlThe solubiliry product of CuS, A82S and HgS and (c) sol- . (d) cH3coo-
10-31,10-44 and 10-51 resPectivcly. The
solubilitiss of these sulPhides are is the order
36. The solubility of a saturated solution of c€lcium
(.l) Ag2S > CuS > HgS (6),{825>HgS>CuS
fluoride is 2 x 10-4 moles Per litre lls solubility
(c) HgS > A&S > CuS (d) CUS > A&S > HgS.
R
product is
EE
t( ll\t l)\l t t j')- (a) 12 x 1o-2 (t) 14 x 1o-'
AR
01 M solutioD ionis€s to
v{ A monoprotic acid in a 0
N
(a) 1.74 x 10-5 (6) 3.52 x 10-3 0.001%. Its ionization constallt is
IA
(c) 6.75 x t0-' (d) 5.38 x 10-2 x l0-3 (6) 1.0 x 10-6
IIT
(a) 1.0
(c)10x10-8 (y'; 1.0 x t0-r2
31. 'lhe solubility of ArX, is y mol dln-3. Its solubility
product is 3t. What is the correct rePresentation for the solubility
(a\ 6 (D 6av' product ofSnS2 ?
va
(c):61 <affiats. tt.t.t: teeT (c) [sn2+l ls2-]2 Irflsn4+l [s2-12
+l
+2. Which of the followi[g can act both as Bronsted (c) [sn2+l [2 s2-12 0dls [2s2-F.
acid and Bronsted base ?
(a) Na2CO3 (D) oH- 39. The solubility of CaCo3 in water is 3 05 x lo-a
(c) HCO3- (d) NH3 molesritre. Its solubility Product will be
(trl.P Pltl l: l9t (a)6.1x 10-' (D) e.3
q3. Which of the following statement(s) is (are) cor- (c) 3.05 x l0-' (d) 9.3 x 10-8
rscl ?
(a) The pH of t 0 x 10-8 M solution of HCI is 8 40. pH of water is 7. When a substance Y is dissolved
in water, thepH becomcs 13. The substance Y is a
(6) The conjugate ba.se of HrPO! is HPOI- salt of
,r{Rs
25. c d
27. 2E, a 31..1 3L c 33. b'c 34, c 35, d
f6. cl 37..1 38. ,
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EQUTLTBBTUM fl (ONrC EQUTLTBRTUM rN SOLUTIONS) 8/83
-
(d) weak acid and weak base (c) Weak acid and its salt with stroDg base
(b) strong acid and strong ba,se (d) Weak acid and irs salt with weak base.
(c) strong acid and weak base Ii.ll t :,11,
(/) weak acid and strong base. ' {A Which solurion wlll be strongly acidic ?
4I. The pH 0 1 M solutron of the following salrs in- (a) wheD pOH=4 5 (6) whenpH = 0
creascs iu the order (c) when poH = 14 .(d) Borh (b) and (c).
(d) NaCl < NHaCI < NaCN < HCI
\(' I)ll T. )tttt,,
(b) HCI < NH4CI < NaCl < NaCN 4t. The?H ofan aqueous sotution ofCH3COONa will
(t) NacN < NH4ct < Nact < HCI be
(a) 7 (b)3
(d) HCI < NaCl < NaCN < NHaCl.
J"T9 (d) 14. tc.PM.T. 20001
49. Which of the followiDg is no, a buffer ?
'42. Which one of the following is true for aly Orproti"
acid, HzX ? (a) HrCOrt HCOI
(a) &z t K,r Ff*r'xo (6) CH3COOH/ CH3COONa
(c) NHaOH/NHaCI
(.) K,, = (d) \"2 = K,r.
* .1afNH.ouzcnrcoon. t r.r.prr.ri.R. 2i)00t
t( B S.Ii. I!.v.'|- 2000\ 50. For a buffer with equal amouots of the salt and rhs
43. The conjugate acid of NHz- is acid with K, = to-t, thcpH is
(o) o (D) 13
(a) NHo+ (6) NH2OH R
tir
EE
(d)8-log2.
lrlirHj (d) N2H.:
Ha4dru C.E.L.T 2000)
AR
("
li. I!,r1.T. 2000) 5.
t R. 51. Iorisation onstant of CH3COOH is 1.? x lO-5
C
44, Which of the following statements aboutpH and and conccntration of H+ ions is 3.4 x 1O-a. Then
S
(c) ls = sr, ./ .C 0.5 x 10-{ mol L-t, then I(+ of tbe electrolyte is
(a) CUS > ZrS > NES In which of the followiDg acid-base titration, pH is
greater than 8 at the equi!€lencr point ?
(b) ZnS > Na2S > CUS
(4) Ac€tic acid versus ammonia
(c) Na2S > CuS > ZnS
is
(c) 1.0 x 10-lo (d) 1.0 x 10-8
product is given ry Ilp. r is gwen in terms of I$ try
C
the relation
of PbIz is 0.0013 M. Then
S
Solubility solubility
N
10-23, 10-20 and 10-54 respectively, which one .,9. The mixture ofacetic acid and sodium acehte, the
\rill precipitate Iirst ?
ratio of concentrations of the salt to the acid is
(a) FeS (6) Mss inqeased ten timcs. TheopH ofthe lolution
(c) Hgs (d) Zns (4) increases by one (6) decreases by one
14, What is tbcpH of 0.01 M glycine solution ? For (c) decreascs ten fold (d) increases ten fold
gb'Eine
K,r=4 5 x 10-3anoK,,= 17x l0-'0at298K E0' Select thepKa value ofrbe strongest acid ftom the
follo ing :
(a) 3.0 (b) 10 0
orl.o (6) 3.0
6E. , 69..1 70. c 71. b 72. b 73. c 74, c 15. d 76.b 77..1
7t. a 79. a
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8/86
t' :.,l!.t,': Nct4 Course ChemistrgWlll
(c) 2.0 t/)1s (,) 1 (b) 5
(c) 8 (d)e
' .p! me pX" of acetic acid is 4 74. The concentration (e) 13 (Keruld C.|a.E.200-l
or CH3COOH is 0 01 M. ThepH of CI{3COOH t4. The principal buffer present in human blood is
(c) NaH2POa + NazHPO4
(b) 4.31 (6) fl3PO4 + NaH2POa
(d) o.414
(c) CH3COOH + CH3COONa
@riss.t _l.L.E. 2t)01
(d) Na2HPo. + Na3Por
tz 50 HCI and 50 mlofo 2MNaOHare
mlof0.1 M
mixed. ThepH of the resultiDg solutioo is
(b) 4.2
l/fircorrucol Ketdln I:M.'l: 2004
65. De8ree of dissociatioD of NHaOH in water is
(d) 11.7o
(.1 & K L.lr.1:201 I .8 x 10-1, then hydrollsis constant of NHlcl is
13.
6 0 001 M KOH means [OH-l = 10-3.
C
ll =-los1o-t+IogI-8
[Hro+] = 10- .. PH = 11.
S
Heuce 14. Ag+ ion is a Lewis acid- CH4 is neither Lcu'is acid
N
7. The solubility incrtases down the Sroup due to nor Lewis base,
IA
''' 10x#=l0ox?M the order : NaNO2 < NaCl < HzS < H2SOa.
.. lHcll = -]- = to-2 t''t. pH = z 17, MnS + 2Hcl* Mncl2 + H2s. As H2s i5 a weak
electrolrte, it ionises very lcss. Heoce coocentration
pll will be > 7.
(c) solutioD is basis,
ofS2- ions is lowered-
(d) 75 ml M/5 HCI = 15 milliDloles,25 mlof M/5
NaOH = 5 millimoles- HCI left unneutralised = 10 1& pH-pKd+t*i#S
nillrmoles. Volume = 100 ml.
=e 30+loC#=e 30
.. tHcrl -ffi=o rru
19. AgI (r) + a4 ;* Ag+
1aq1+t- 1aq1,
PH=-lo8(0 1)=I ryn1 Na+ + I-. Due to common ion effect,
10. On dilutioD of a weak aoid soiution, percentage -
equilibrium shifts backward.
io8isation iDcrease&
'lls
E0, a t1. a 1t2. c ltJ. I ll'l e E5. d
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EQUtLtBRIUM (tONlC EOUtLtBRtUM tN SOLUTTONS) 8187
-
20. NaCN is a salt ofweak acid (HCN) and strong base 29. .r (Cus) = r'-K, = y'ro=f = lo-ts s,
(NaoH).
AgrS ...- 2Ag+ + S2-,
Hence
Kro = 1z s;2 x r- 4,r3
,r=\E =
l0- 14
(1.3 x lo-e) x 1,/ 80
or ,= lt -- \r/3
= 2'48 x 1D-2 [a \nJ
. . %age hydrollsis L ^-41\t/3
= (2.48 x l0-2) x lfi) * 2.48.
= l!,-l
t-t = 12 5;r/3 x lo-r5,
22. If-r is the solubility ofAgCl in 0.04 ,'| CaCl2, then r'R;
.r (Hgs) = = v10-54 = 10-27
[Ag+] =: rn L-1, 30. The dislociation mnstants of a weak acid and irs
"t conjuBate base are rclated as
[Cl-] = (0.04 xZ) +x-0.08 pK"+pKb=pK-
.. t(0 ft])=4x 10-lo . plL + 10.83 = 14
or -t = 5.0 x 10-9 m
or PIq = 3.17
ICH.COONaI
23. pH = pKo + log -torKe=317
lc-Ee-Oo_Hi or logK,- -3.17=483
ICH.COONaI
5.5=4.5+ros-_lo-j1-: or x to-4. &=6 7a
stroDgest base.
c(1 -a) ca
N
ca,
25. Sulphides of Group II (PbS) haw low solu\ility
IA
_ ro-11 =
1.7 x l0-' protons as well as given protons.
S
N
52. In R-NH2, electroo pair otr N is mosl easilyavail- 65. ln the rcaction 12 + l- I:-, I- is the electroo
-
pair doDor and hence is a Lcwis base.
able for protoDatioD besause R iselectron releasiDg
grouP. 66. In group III of aDalysis, addition of NHaCI iD-
s. After dilutlo[, [H*l = lo-o t 2. creases NHo+ ion concentration aod decreascs
_ to-ta
10-4
l2 _2 x l0-ro M ''Y + M2+
sZs
+ 2X'
ln the final solution, I<le = (r) (2 s)2 = 4't3
lH+l - (10-6 + 1o-3)/2 =4x(o.5xto-4)3
t0 "
-...--z-
r.001 x
- 5 Y 16-13.
68. pH > 8 at the equivalcDcc poinl means that thc sali
= O.5oo5 x 10-3 - 5 005 x 1o-4 formed oB hydrolysis sbould give basic solulion r'.e.
whell acetic acid reacts with NaOH.
pH = - log [H+1 - log (5 005 x 10-1)
=
=4 -0 6994 -3'3 69, Due to thunder storm, temperature increases ie,
pu =pr! + rogffi IH+l increases which meanspH decreases.
70. For salh ofweak acid aDd wEak base,
o, rosffi=s8-4'8=10 q = K_/rt Kb_
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EQUILtBBtUM (tONtC EQUtLtBRtUM tN SOLUTTONS)
- 8/89
71. Total [I-] = lo-4 + t0-6- 10-1M 7e. Isr crse. ?H =/rq + tos#ffi =,/,Ka + k)c
lAs+l II -l = I(p
2nd case. pH =fK, + fog1p
.. [Ag+l I10-4J - 1.0 x 10-16
or [Ag+l = t0-12. =pKa + logf + tog10=pK, + togf + r
72. Pbl2 P*+ +21- t0. tligher the I(s r"lue or lowcr the pK, value,
- stroDger is thc acid.
..[Pb2+]=l3xl0-3M Itl' cHrcooH :-' cll:cro- + H+
Il-l=2x 1.3 x 10-3M =2.6 x 10-3 M
c00
&P = tPb'z+l [-F a
c---< ca cu
= (l 3 x 1o-3) (2-6 x 10-3)2 K,=.ffi= ;:;-c":."=,TV
.. ca.c4 ctz
= 8.8 x 10-9.
lrr+l=ca =, "T7; ="Tj
73. The one with lowest value of qp ie. HgS wi
prccipitate out first. irll - IoglH+l = - Iog(K,c)r'2
74. Gtycine H3N+CH2COO- is morc acidic than = x. - tog.1
| I-r,,s
basic, IDstead of K, !"lue, the second giveo Ka
value Is mrrEsponding to the K6 value 1r". - togc; =f
= 1l ,z,r - ros ro-21
(. I! x Kr = 10-la;. Hence overatl ionizarion
=!*a.t+ = t.tt
mnstant,
tZ
R
EE
50mlof 0.1MllCl =S0 x 0.1 uri[imotes = 5 o]it_
K- xK- =4.5x 10-3 limoles. 50mlof0.ZNaOII = 50 x 0.2 millinl(rcs
AR
pOI{--tog(5x10-2)
- pH = - log (0.87 x l0-7) = 7 - 0.93 =6.07
IIT
7s. pH = p\
* bc Iggqffd-I@ (see pase 8/51) :--1-
= rog
5 x t0-;'
= IoS 20 - I 301
pH=14- t.301 = 12.699 = t2.10
:.pH-pKrn=t"ci#t
ll3. 0.365 g HCt = !-!€ mote = o.o I motc
76. Hydrollsis reaction is X- + H2O
HX + OH- =:+strong
For a salt of weak acid with
100 cm3 of 0.2 M Naoll _
*# x loo = 0.02 r.rotc
base, NaOH left unDeutralized = 0.01 molc
.. K_
r\b=K-=ca'
Volume of solution = 100 ml
.- Molarity of NaOH in the soturton
t0-14 0 0r
. j-_-?=0.1 xotoroz__ l0-8616 = 16-l =ffix1ooo=o tM=10-rtu
% hydrolysis = 10-4 x
. IH.l -#i;= 10-rrM
100 = l0-2 = 0.Ol
77. MX1 (D \-= M4+ (aq) + tx .. pH=13
@q)
, 4.t K* l0-t4
K,p =.r x (4.r4 = 256ss qs = 1K,ot 61t/5
= 5.55 x 10-10
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8/90
Neu) Course Chenistrq
ADDITIONAL
As e erLi on -F.,e as on Typ e Q.u e sti ons
n. rvhile onswerlng these
oDe of th
(d) If both AEertloD atrd R€osou are truc lnd the u of the Aaslrtiott'
(ri If both Assrrtlon rnd Reoson sr. true but reason is not a corr'tt cxPlanetlon of the 'Assertlol''
Assertion Reason
6. pH valueof HCN solution decrEases when NaCN NacN provides a common ion cN- to HcN'
is added to it.
pH of e,arcr increas€s with increasc in temPera- Iq/ ofwater increases with iDcrease in tenP€rature'
ture.
buffer solution resists the changc in
when a small amount of stroog acid is added to Buffer action ofthe
added ro it.
a buffer solution, it! PH value docs not cianSc pH when
some acid is
significantv.
I to resist the An aqueous solution of ammoniurn acetate can act as
A buffer solutions has caPaciry
change inPHvalue oD additionofa smallamount buffer.
ofacid or base to it.
10. Sb (III) is not preciPitated assulPhide when in its Tbo coocentration of 52- ion in atkaline medium is
alkalina solution, H2S is Passed. iDadequate for PrcciPitation. lA.I IJL,1S' 2004)
11. AdditioD of sitver ioDs to a mixtur€ of aqueous Ilp of Agcl < Iqp of AgBr. Q4.I I'M'S' 200')
sodium cbloride and sodium bromide solution
will first preciPitate AgBr rather than ASCI'
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EQUtLtBHtUM (toNtc EQU|L|BB|UM lN SOLUTTONS)
- 8/91
True/False Otatemenis
Whic h oI lhe folloh'ing bremeny
s ore fahe ? Ret+,rite 5. A_ solulion with pH less thaD zcro or greater than
rhem conectly.
14 cannot be prepared.
l. The degree of ioDization ofa salt is directlypropor-
6. More_acidic is the solutioD, grca(er is itslH.
tional to its molar conc€ntration
7. ThepH of lo-E M HcI sol;rion is 8.
2. A Lewis baseisa substaDcewhich carldonate a pair t. Ionic product of watcr is ah,ays cqual ro l0-14.
of electroos. 9. PhenolphthaleiD is not a suitale iDdi€tor for ritru_
3. CO2 is a Lewis basc. lion of HCI solution wiih Na2CO3 solutioD.
4. The ionic product of warer 10. Tbe solubility of pblz in watcr dccreases if KI
changes if a few drops is
ofacid or base are added to ir. added to it.
Columr A columr B
(4) fitration ofacetic acid with NaOH solurion
C
(6) Pbenolphrhatein
N
1,3,4,6,7,8.
FILL IN THE BLANKS
l. an electrotyte 2. inversety, squarc rmt of molar coDccntratioD J. donate a proton, acc€pt a proron
4. conjugate s.pOH 6. acidic 7. saturared. t. 12
HINTg/ExPLANATtoNgtoAe9,ert,ion-Reagonrvp"9:"=!iong
of HrO is smatl because 7. p]Hofwater decreases with increase in tenrpera-
,. ,"*r"" .f ionization
Hro is1*'y*t?5"1'rictrolvte' 10. sb (III) is precipirared (in Group IIB) by HrS in
j. pH = pKo + log
3' fridT'
il{cidT' acidic medium (dil. HCI). In acidic medium, s2-
At nrid point [Satt] = [Acidl. concentration decreases so that radicals of Group
4. Numberof fitrataUtepiotonsinHCl isgreaterthan IV are,ot precipitated. In alkaline medium, 52-
present in acetic acid. ion concentration increases and not decreascs.
5. weak acid has a strong conjugate base' rr. I(, of Agcl > Kro of AgBr. For precipitation to
6. gCN + H+ + CN-. NaCN gives common oc'cur, ionic proOuct should exceed solubility
CN- ions. Equitibriunr shifts backward, [H-] Product.
decreases so thatPH increases'
R
EE
AR
C
S
N
IA
IIT
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R-edoxReactione
1d ion-electr
,., R
EE
.-j1!_.1_!1,9l_!a:1,,,:1,1i:,:'',|:.i]ii,':li:l1i,jo+j,,-,Ii
:
AR
H2SO4, CH3COOH etc.) combinewithOH- ions of ol ltydntgen or any oher electmpositive eleme4t.
S
For example,
N
salt ard weakly iodzed moleculas of water. In this (i) 2Mg(s) + 016) ----------.' 2Mso(r)
IIT
Q4ddition of orygen)
(ir) Mg (s) + Ct G)......- rvrecrz (s)
(Addition of electnnegative element, chloine)
(,,r 2n S
G) + 016)......+ zs(s) + 2Hroo
(Removal of hydrogen)
(t)4@d+Hro(O+orG)-
zKoH(aq) + I2(r) +or@)
(Removal of electmpositive element, potassiunt)
-. _In all these reactiotrs, the compound under-
lined has undergone oxidation.
. 922. . Oxidising agent or oxidanL According
to the classical concept,
examples of redox reactions, Before we discuss these Ar oddlsiDB agrrl or of,ila[lit a srt'/la*euhtch
redox reactions in detail we must be familiar with the ot arr! oth?r elaroiwgtitc eb-
concepts of oxi&tion and reduction.
fj_!:!i""-R".1,,,.,, -. a 1.r.. j Con..pf
-' _ rar ,,,::,r::l
chlorbrc
AR
For examPle,
N
ot
N
2Me+O2-
IA
IIT
I
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914 NetX Course Chemistrq
Further since, reducing agents donate electons Here, Al rcduces F%()3 to Fe while itself gcts
to other substnac€s while oxidising agents acc€pt oxidised to A[1C)J. Conversely, FerO, oxidises Al
eledrons from other substancqs, lherefore, ruducing
ggents are ele{,,ron donors whik oxidising apt*an toAlrO, whilc itselfgets reduced to Fe. Therefore,
electron accrptors. ln other words, reducing agents Al acls os a reducing agent while FerO, acts os a,t
Xter reducing other substancqs thenselves get oxidising ogent.
oxidised while oxidising agents after oxidising other
substanccs thernselves get rcduced ia the process.
From thc above discussion, we conclude:-
Let us now reconsider the two reactions (be-
tween Mg & O, and Clr) discussed above in the Oxidalion iJ a process in whith one or more
light of reducing and oxidising agenrc. elcctrons ore losl.
In the reaction of Mg with Or, Mg gives Reduction Lr a process in which one or more
electrons qre gainad.
electrons to orygen which gets reduced to 02- ion
while Mg gets oxidised to Mg3+ ion. Conversely, Oxlda[t rJ a substsnce which can sccepl one or
more electrons,
02 accepts electrons from Mg and gets reduced to
Reducant rs d sursrazce which can donale onc or
()2- ion while Mg gets oxidised to Mg3+. There- more elcclrons.
forc, Mg is a reducing agent while O, is an oxidising
agent. Sitnilarty in the reaction of Mg with F, or In a redox reaction, oxidant is reduced by ac-
ceptinq electrcns and rcductant is oidised by losing
Cl2,Mg acts as a reducing agenl while F, or Cl, elcclrot$.
behaves as at oxidising sgent. For further illustra-
tion, consider the following reactions : R Using electrcn trqnsfet idetiily
---------I
EE
Oxidised
the oidant snd reductant fu the following redox
(D HzS +
AR
(N.C.E.R.T.)
IA
Here, HrS reducrs FeCl, to FeCL while itself Solution. Each atom of zinc loses two
IIT
gets oxidised to S. Conversely, FeCl, oxidises IlrS electrons to from Zn2+ while each atom of orygen
to S while itself gcts reduced to FeCl2. Therefore, accepts these two electrons to form oxide ion
HrS acts as a reducing agenl while FeC\ acts os sn (O2-) as shown below :
oxidising agent .
[-oxidised--l zr,: +ll:o: ], .-----_ ,r'* [,9,'-]
(ii) Al + F%o3 ......., Al2O3 + 2Fe
(Red!/cin9 (oidisins Thus, Zn acts as reductant (ot reducing agent)
agcnt) n ond orygen scts as an oxidant (oxidising agent).
ogent) |
I p"4u".6____J
Using electron-transfer concept, identiS/ the oddant aDd reductant iD the following redo( reactions.
(o) zn(s) + zlj+(aq) Znz+(aq) + uz@) (N.c.E.R.T.)
-
(6) 2{Fe(CN)6la- (a4 ) + H2O/r,q + 2H+ (oq) EFc(CN)613-(zq) + 2Hz)(dq)
-
(c) 2[Fe(CN)6]3-(44) + 2oH-(4q) + H2o2@q1 2[Fe(CN)6]{-(4q) + 2HzO(O
-
(d) Bto; (aq) + F;,g) + zou- (aq) Bro;(as) + zF-(aq) + H2o(t)
(e) 2NaClO. 1ag) + tz@4) I -
2NaIO3(aq) + cl2G)
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REDOX REACTIONS 9/s
Reductanls r (a) zn (b) [Fe(cN)614- (c) H2O2 (d) Brot (e) Naclo3
9.4. classilication ol Bedox Reactions':+;irr;:'iil'::i':ii;:i'ii ln this reaction zinc acts a reducing agent and
reduces Cu2+ to Cu metal by transferring two
All the redox reactious may be divided into
electrons.
the following two tyPes :
Thus. durins this redox reaction, zinc gets
oxidiscd to znz+ ions while Cuz+ ions get reduced
,f#:,f,#;;# to coDDer metal. On the basis ofthis redox reaction,
rcactions' For ex-
-- all the'above observations can be easily explained :
'anple, -
(i) Since zinc is being oxidised to Zn2+ ions
(i) Displacement ofcopper from CuSOo solu-
which go into solution, therefore, zinc rod starts
tion when a zinc rod is diPPed in it. dissolving.
(fi) Reduction of HgCl, to HgrCl, by SnClr' (ii) Since each Cu2+ ion accepts two electrons
(b) Inrlirect redox reactlots. Redox reactions lost bv zinc. therefore, Cu2+ ions are reduccd to
in whiih oidation and. reduction take Place in dif' copper metal which, in turn, settles down at the
ferent vesseh sre called indirtct redox rcactions' bottom of the beaker'
hhese hdirect rertox reactions form the basis of MathematicallY,
clectrochemical cells' R Loss in wt. of zinc rod
-
Eq. wt. 9f zinc
EE
Wt. of copper deposited Eq. wt' of copper
9.5. Direcl Redox Reactions-Oxidation'
AR
sulPhate
N
inibeaker A sPon- ner metil. the blue colour of the solution which is
IA
form Cu2+(aq) and SO!-(aq). When zinc rod is Simitarly, when a copper rod is placed in a
solution ofsilver nitrate in abeaker, we observe that
dipped in CuSOo solution, the following redox the solution againDeco
reaction occurs :
dissolving. This is apP
oxidation (loss of 2z-) solution which was
f 1 chansins to blue due to thc oxidation of Cu to
zi1s1 + cuz* 1aq1 --- Zn2+ 1a,.)+Ctt1s1 Cu2+"io;. At the same time, Ag+ ions get reduced
t' to silver metal which in turn, settles down at the
LR"ao"tion (sainof?z-) _J bottom of the beaker [Fig. 9.1 (b)1. The overall
redox reaction may be written as follows :
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9/6 Neq' Conrse Chenr istrq
Oxidation (loss of tu-)1 than rut ol Cuwhile electron donating ability of Cu
;- is mole ths.n lhat o[ Ag.
Cu(;) + 2Ag+(aq) ......._ Cu2+(aq) + Ag(s)
I R",lu"tio, (sain of k-) J "(i')
A large numbcr of redox reactions occur in
FIGUBF;9.I.
'|,,
(a) Znc dirsolves to form Zn2r iors
wh.ite Cuz+ ions geI reduced to copf,er metal lrfiich
setflrs down in torm of finc padides at the hottom
of the heaker. R
EE
(b) Copper dissdves to form Cu2+ ions while Ao+
iors get reduced to silver mptal whicn sc-tties ao',in
AR
. In this reaction. copper acts as a reduces agenl ost during oxidation are
S
electrons-
IA
@xidation)
HrO. (aq) + 2e- ......., 2 OH- eeduction)
MnSO4 (4q) + 5/2Fer(SO), (aq) + 4 H2SO. (l) Sn2+ (a41 + zHe+ @d--,
Sna+ (aq) + zIJg+ (aq)
To eliminate fractional numberg multiply the
entire equation by 2. We have, Suppllng the required spectator ions, we
have
R
2 KMnOa(aq)+ 10 FcSO4(aq) +8 H2SO{aq)
EE
+ 5 Fe2(SO.), (aq) + - (0
H2o
SnCl2 (aq) + ZHgCl2 @d
2 MnSOn (o4) 8
-
AR
equations :
(vi) Self oxidation redl.ction oI Clzin prcsence
S
Cl2 @)
2 sroS- (a{) ""'- s .cl|' @q) + 2 e-
IIT
(reduction)
(oxidation) Clz @) + tZ OH- (aq)
l, (aq) + 2 e- '------t 2l- (oq) Qeduction)
-
2 ClO, (aq) + 6 HrO (l) + 10 e -
(oxidation)
Overqll red(N rcactio,t I
2 CS+ (aq) + 7 },,zo (t) (oidation) Supplying the required spectator ions, we
have,
so2 G) + 2ld2o (t) ---) 3cl2@) + KoH (aq) ....t
6
Sol- (aq) + 4H+ + Ze-lx3 (reduction)
s Kcl (aq) + Kclot (aq) + 3 Hro (t)
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9/8 Neur Course Che nt i stry
FORiP.KA,efflep r,:
following redox 2. Split the tollowing redox reactions irl the oxidarion
and rcduction half reaclions.
(a) Fez+ (aq)+2t- (oq)- 2Fe2+ (otD+tz@q) (a) 2K (r) + ctz@) ......- 2Kcr (r)
(b) Zn (r) + 2H+ (04)- Znz+ (aq) + HzG!) (b) 2N (t) + 3Cu2+ 1aq1
(r) ..*
N
..Reduction
- ...O verall redox re ac ti on
9.7.1. Rules for asslgning Oxidation Num- (D) Since fluorine is the most electronegative
bers. element known so its oxidation number is always
The following rules are applied to determine - L in its compounds i.e. oxides, interhalogen com-
the oxidation number of an atom in an ion or a pounds etc.
molecule. (c) In interhalogen compounds of I Cl, Br,
l, The dcidalion number of all lhe atoms of and I ; themore electronegative ofthe two halogens
dfurent elenVnts in thei respective eiementary slales gets the oxidation number of 1. For example, in
-
IF7, the oxidation number of F is 1 while that of
and allotropic forms is taken to be zero. For example, -
in Nr, Clr, Hr, He, Pa,56, 02, 03, C (diamond Iis + 7. Similarly, in BrClr, the oxidation number
or graphite), Br, , Na , Fe , Ag etc., the oxidation of Cl is - 1 while that of Br is + 3.
number of each atom is zero. 7. In neutral compoun^, the sum olthe Nida-
2. The oidation rumber oI a nnnootomic ion lion numben of all lhe aloms is zem.
is the sa,ne ds lhe clntge on it. For example, oxida- E. In comples ions, the sum of tlrc oidation
tion numbers of Na+, Mg3+ and Al3+ ions are * 1, numbe$ of qll the atoms in the ion is equal to the
+2 and +3 respectively while those of Cl-, S2- cho,ge on the ion.
and N3- ions are -1, -2ar,d -3 respectively. With the help of above rules, we can lind out
3. The oxidation number ol htdngea is -+ I the oxidation number ofany elenent in a molccule
when conbined with on-melols snd is I when - or an ion. Metals invariably have positive oxidation
cbnibined wiih active mitaE calted mefiffri,ilrides numbers while non-metals may have positive or
nat as Lin, KH,Wgryr; eary'e-tc. negative oxidation numbers. Tlalsition metals
" 4. The oidation number of otygen is -2 in usually display several oxidation numbers. The
highest positive oxidation number for s-block ele-
most of ils compounds, ercept in peraxides like R
EE
' HrO, BtiOretc. where it is ments is equal to its group number but forp-block
L .Another interest-
-
,
elements it is equal to group number min*s l0
AR
ing'exception is found in the compound OF, (except for noble gases). However, the highest
(orygen difluonde) where the oxidation number of negative oxidation number forp-block elements is
C
orygen is +2. This is due to the fact that fluorine equal to eight nrinzs the number ofelectrons in the
S
N
being the most electronegative element known ha-s valence shell. In other words, the highest positive
IA
5. In compounds Iormed by union oI metak periodic table. For example, in the third period, the
with non-metals, lhe metol atoms will have positive highest positive oxidation number increases from
oidalion numben and the non-metals will have + I to + 7 as shown below :
negolive oidation nurzbers. For example, Na+ (+1), Mg2+ (+2), Al3+ (+3), si (+4 as
(a) The oxidotion number of alkali metals (Li, in SiCl., SiO, etc.), P ( + 5 as in PF5 , PaO,o etc.), S
N4 K etc.) is always + 1 ar 7 those of alkaline eaah ( + 6 as in SF6, SO3 etc.) and Cl ( + 7 as in ClO, or
ntetals (Be, M& Ca etc) is + 2.
CIO.- ion).
(b) The oxidation number of hologens (f;, Cl,
Bt; I) k ulways - I in metat halides such as KE As stated above oxidation numbers are also
AlCl, MgBr, Cdlr. etc. called oxidation states. For example, in HrO, the
oxidation number and oxidation state of hydrogen
6. In compounds formed by the union of dif-
is + l while that of oxygen is -2.
ferent elemenls, lhe more elecEonegative otom will
have negalive oidation rutmber whereas the less We shall now illustrate the use of above rules
electronegotive qnm will have poitive oxidation
in determining the oxidation numbers and also for
numben For exzmple, identi$ing the reductants and oxidants in redox
reactions.
(a) N is given an oddation number of -3
when it is bonded to less electronegative atomasin l,lx-{i\l PLtt 9.2. Calculs,e the uidation num-
NH, ard NIr, but is givcn an oxidation number of ber of (i) S in HrS, (ii) C in CO, (iii) C in CHzClz,
+3 when it is bonded to more electronegative (iv) N in (NH).SO|, ft) Pb in PbrOrand (vi) P in
atoms as in NCl3. NarPOo.
L
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9/10 : ,., . Neto Coursc Chemistrqlft[)
Solutio!, (i) S in HrS. Lct the oxidation /r+r\ -z
numbcr of S in H2S be x. Writing the oxidation (N n. J, so.
number of each atom abovc its symbol, (. Oxidation numbe r of SOI- is -2)
+l .r . . Sum of oxidation numbcrs of all thc atoms
Hzs in (NHo), SOo
(.
Oxidation number of H is +1)
= 2x+2(+ I x4)+(-2)= 2x+O
Sum ofoxidation numbers ofvarious atoms in But the sum of oxidation numbers of all thc
H,S atoms in (NHa)rSO n (neutral) is zero (Rule 7).
= 2(+1)+x= 2+x .. 2x+ 6= 0or.r= -3.
But the sum of the oxidation numbers of Thus the oidation nunber of nittogerr irt
various atoms in H 25 (neutol) is zero (Rule 7). (NHo), SOo is -3
-'. 2+x = 0 or .t= -2 ,(v) Pb ln Pb3O.. Let the oxidation number of
Thus tlrc oidotion ttumber of S in HrS is -2. Pb in PbrOo be .r. Writing the oxidation number of
n (il) C in CO2. Let the oxidation number of C each atom above its symbol
in CO, be .r. Writing the oxidation number of each x-2
atom above its symbol, Pb: 04
x -2 ( . oxidation
number of O is - 2)
coz .'. Sum of the oxidation numbers of all thc
( .' Oxidation number of O is 2) atoms in PbrOo
- R
. ae4= 3v-s
EE
.'. Sum of the oxidation numbers o[ various = (3).r+
atomsin CO2 =x+2(-Z)= x-+
AR
:. x-4= 0 or r= + :
N
r (iii) C in CH2CI2.Let the oxidationnumber of (vi) P in NarPOo. Let the oxidation number of
C in CHrCl, bex. Writing the oxidation number of P in NarPO. be.r. Writing the oxidation number of
cach atom above its symbol, each atom above its symbol,
r +l -l +1 r -2
c H2 cl2 Na, P On
zer(t +5
r (iv) N in (NH.)2SO.. Let the oxidation num- ) \i 1t\u,!.1' ,t t. Calculate the oxidation num-
ber of nitrogen in (NHo)rSOo be x. Writing the o!
ber
oxidation number ofhydrogen above its symbol and (i) N itt NOt ; (ir) P in H3P2O; (iii) C i,t
that of SOI- ion above its formula. Col-, @) Cl in Ctoo antl (v) Crin C4ol-.
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REDOX HEACTIONS 9/1 1
(. Oxidation number ofH is + 1 and But the sum of oxidation numbers of all the
that of O is atoms in CrrO]- is equal to the charge on it, i.e.,
-2) R
2 (Rule E)
Sum ofthe oxidation numbcrs ofall the atoms -
EE
in HrPrOr- .. 2x-74= 2 or x= 6
AR
atoms in H3Pz 07- is equal to the charge present on tlXANfi'Lll9.1. Whatis the the oxidqtion num-
N
b;et
it i.e. - 1 (Rule 8)
-. 2x- 11 =-1 orx= (i)
IIT
..
in [Fe(CN)5la- = .r + 6(- L) = x e -
Sum of the oxidation numbers of all thc
atomsinCO]- ion = r+ 3(-Z)= x-6 But the sum of oxidation numbers of all the
tl atoms in Fe(CN).la- is equal to -4. (Rulc E)
luu
lal
atoms in
But the sum of oxidation numbers of all the
COI- ion is -2 (Rule 8)
:. x-6: -4
Thus the oidation number
or x=12
ol Fe in
l-+ .'. x- 6: -2
IFe(CN)51'- r:r + 2.
or x= * 4 (ii) Mn in MnOt. Let the oxidation number
nrus he oxidotion stqte of Cin COrz- rl +4
of Mn in MnOn- be r. Writing oxidation number of
t (lv) Cl in ClOa. Let thc oxidation number ol'
each atom above its symbol, we get
Cl irr CIO; ber. Writing he oxidation numbers o[
each atom above its syrnbol, Mn o4
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9112 Ner4 Couyse Chemistrq
.'. Sum of the oxidation numbers of all the .. x-8 = -l
atoms in MnOo- = x+4(- 2)=x-8 or x= +7
But the sum of oxidation numbers of all the nlus, the oidqtion number ol Mrt inMnOo is
atoms in MnOl- is - 1 (Rule t) +7
,
EE
9Hz 0 o (2) - 2(7)/2 = - 1
cH2o ) I I t(2)-2(1)/1=O
AR
HCOOH ) ,,
I 2 Q\ - 2(1't/1= + 2
C
r:i l. Ifa comPouDd cootains two or more atoms ofthe same element, the O.N. determined by the application of
S
the ab@e rules is oDly an average of the o.N. ofall the aroms present io the molecule. f6r exaniite, o.N. of
N
The aclual c0ddation numbers of indMdual atoms crn, horet/er, be determiDed if the stoich iometry or the structu re
of the compound is kno$m as disqrsed uDder Additional Useful Infonnation
for Cornptitive Ex;nination.
FaRiP- I],CE
l. "RA?LEMS
Find the o(idatim number of the elemcnt in bold
iD the follo$dng species :
5, Find out the cxidation number of sulphur in the
following species :
O SiHl, BH3, BF3, SrO!- BrO.- and HrOo2- (NH4hsol, H2so1, s2o42-, szo?-, Hso3- and
(N.C.E.R.T.)
r{so;. (N.c.E.R.T.)
(u) Pbso4, u2or-, B.o?-, crol-, rqMno..
2. Determine lhc midation numberof 6. Dctermine the oddation number of all the atoms
C in the fo ow-
ing :
in thc following well known Gidants
KMnO., KrCrrO, and KClOn.
qH6, ClHlo, CO, CO2 and HCOt. (N C.E R.I; N-C.E.f.T.)
7. DetormiDe the change in the oddation Dumber of
3. Detetmine the oddatioo number of O in the fol- S in H2S and SO2 in the following industrial reac-
lo iog :
tion :
oF2, Na2o2 and CH3cooH. (N.C.E.R.T.)
4. Find out the crddationoumber of CIio HCl, HCIO,
2H2S G) + so2 G)- 35 (s) + 2HzO (J)
(N.C.E.P.T.)
CIO;, CaOCl2 aDd Cl02. (N.C.E.R.T.)
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REDOX REACTIONS
9113
EI<S
1. (,) si = - 4 insiHo, n = - : in n{ I *1,,* 4. O.N. of CI =-linHCt,+linHCIO+7in
BF3,S = a 2inS2O3-, Br = + 7in BrO; and ClOt in CaOCt2 and + 4 in CIOz.
p=+5inHpo?-,
5. O.N. of S = + 6 in (N I I4)2SO4, I,I2SO4 and
0i)S = + 6inPbSOa, U = + 5ioU2Or-, B = + HSoo and SrO?-, + 4 in HSO3- and + 3 in
3 iD B4O?-, Cr = + 6 in CrO?- and MD
= + 6 ir szol-.
K2MnOa.
2. O.N. of C = - 3 in
eHe, -2.5 in C4Hr0, + 2in 6. K= + 1,Mn = + 1,O = -Z;K= + l,Cr=+ 6,
CO, + 4 iD CO2 and + 4 in HCO'.
O= -Z;X= '1,
+ Ct = + 7,O = -2.
3. O.N. of O = + Z io OF2, - 1 iD NEO2 aod _ 2 7. O.N. of S changes from - 2 in II2S and + 4 in
in CI{rCOOH. SO2 to zcro in elentental sulphur.
e.u Hedox Heactions in Terms Here, the oxidation number of iodine in-
creases from _ 1 to 0, es
from 0 to _l while tha n_
changed. Therefore,Ill is
In terms of oxidation number, teduced to Cl- ions.
C)xidatio R 1-Oxidised--1
+4-200+3
EE
in which -2
number of an a,om or alom^s while reduction mo, (l)3Mn Or+4Al .-..........,3 Mn + 2AIz o3
AR
For further illustration, consider the following _ 93?: O:ddising and Reduclng agents in
examples. terms of Oddatlon Number
+'t -1
,-- Oxidisedl
0 0 +l _l
(i) 2H I+Cl2-Ir(s)+2H Ci
I R"do"".t t
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Pradeep's
9114
- 1 in ion.
Thus, there is no change in the O N' ofH and
C
Zn tcts ss a reductanl.
The O.N. of N decreases from + 5 in NOt to
IIT
Therefore, KCIO, ako ocs on oxidising agent -3 in NHf, and, therefore, it is reduccd and hence
Reduclng agcDts or
NO; acts as lhe oxidqnl.
ing agents are electron (b) Writing the O.N. of all thc atoms above
electrons causes a corre their symbols, wc havc,
oxidation number, therefore, according to the 0 +l-2 +l-1 0
3.
4. 4.
6. 6.
R
EE
AR
C
S
The compounds of metals which show more CuO, it is *2. Therefore, these two oxi<Ies are
IIT
4 Mg(NOr), (ag) + NrO G) + HrO (D ..(r,, on L.H.S. of Eq. (i) but onlyone in Ct'+, the refore,
mulriply CP+ on R.H.S. ofEq. (r) by 2 an<l thus the
oms on R.H.S. total decrease in O.N. of Cr is 2 x 3 = 6
, therefore, to Step 4. Balance increqseldecrease in O.N.
cient of HNO3
Since total increase in O.N. is 1 and decrease
of Eq. (ir), we is 6, therefore, multiply Fe2+ by6. Combining sreps
have, 2 and 3, we have,
4 Mg (.r) + 10 HNo3 (aq) ......- crzo4- @q) + 6Fe2+ 1aq1..-
4 Mg(Nor), (aq) + Nro G) + Hro (f .. (iv) zcp+ @q) + Fet+ (aq) ...(ii)
Step 5. Balance O ond H atoms by hit and frial Sttpi.Balan H andO.
mellrcd. To balance Fe on , multiply
30 orygen atoms on L.H.S. but Fe3+ on R.H.S. of
gnly s on R.H.S. of Eq. (iy), rherc- crrol- @q) + 6 Fez+ 1aq1+ H+ .....*
fore, omq change tbe coillicient of
Hzo have, z0f+ @q) + 6Fe3 (aq) ...(iii)
a Mg (s) + 10 HNo3 (a4) ......- Step 6. Balonce O otoms by adding HyO
R
molecules. Sincn tberc are 7 O atoms in CrrO] - but
EE
a Mg(Nor), (aq) + N2o
G) + s Hro (f ...(v) only one in HrO, therefore, to balance O atoms,
AR
+6 -2 +z 3+ i+
I Cr, o7 f2- (qq)+Fe (qq) + Cr (oq)+Fe taq)
|l,u
C).N. decreases by 3 per Cr atom
The
Stcp l. Wite the skeleul equstion.
uation for the given reaction is :
mor- (oS) + Br- (aq).......t
Total decrease =2x3 =6
Here O.N. of Fe increases from + 2 in Fe2r MnO, (s) + BrO3- (aq)
to + 3 in Fe3+ while that of Cr decreases from + 6
in CqOl- to + 3 in Cf +. . St p 2, Find out he elements which tutdergo a
change h oriilafion number (O.N.)
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9/18
o.N. iDcreases bY 6 Per Br atom Thus, Eq. (v) reprcscnl.s the correct balanccd
+'7 -l
!---------1,
+4 +5
equation.
1 \ \\ il'i l 'J ' Bulu ce the oxidation reduc-
togetJrcr
Sten 5' Balance all oton$ other lhan O ond H'
C
MnO2 bY 2, we have,
Indicating thc increase ancl decrease in oxida-
IA
zMnof, (uq) + Br- (oq) ' tion numbers in each case, we have,
IIT
or Mnof (,q) + Br- (aq) + H2O (/)----"') 226 must be faciorized in such a mlnner that thcy
2N'tno2 (s) + Brof (aq) + zoH- (aq) "'(v)
b"co.e purts of ferO, and SC)r' Rearranging, Eq'
(iu), we have
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REDOX REACTIONS
9/19
+2 -1 +3 2_ +4 2_ TIE tn)o half reactions are then aclded ap. These
4 [Fe +S2l+ 11 02 [4 Fe +6 ol+[8 s + 16 Ol
--.] rules are illustrated by the following cxamplas.
or 4 FeSz + 11 Cl2...-2FerOr+gSO, Pemantonqte ion reacts with
medium to give Fe3+ and
. This represenls the required balanced equa_ ced chemical equalion for lhe
tron. (N.C.E.R.T.)
II. Ion Electron Method or Half-Reactioo l. Write the skeletsl equation
Method lot th
MnOa (aq) * Fe2+ (aqy--...t
}./.nz* (oq) + Fe3+ (aq) ...@
equal to he electrons gained duing reduction hatf Step2. Wite the O.N. of alllhe elcments ubove
rcaction. The vaious steps involved in this method lheir respective symbols.
are :
+7-2 +2 2+ 3+
(Mno4)-t + Fe Mn+Fe
Step 2. Frnd out lhe species which orc uidked
and which are reduced.
O.N. increases by I per Fe atom
stcp ha| Step 3. Fnd out the species which have been
,eactions, tion R
oidised aad reduced ond split lhe given skelcton
EE
haf reaction .
equslion into two haf reactions,
AR
oxidation number
Thus, the above skeletal Eq. (i) can be divided into
IIT
f"liTlli:
_.... Slap 5, To balatcc thc tzhrction ha{ eq.ation
(iii)
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(i), we have,
Mn2+ (arJ) +4H2O (aq) "'(vii\ +3-2 +5 0
C
half equation.
IIT
+ 8 H2o (/)
As2S3 (s) 2 A sof,- @q) Step 2.Witc he O,N, of all the elements above
-
+ 3 S (s) 16 H+ + 10 e- ...(vi\
theb rcspective sylb ols.
O.N. of Cl increascs by 5 per Cl atom
The H-atoms get automutically biilanced. v
Thus Eq. (vi) rcprescnts the balanccC oxidation ol -1 +5
half equation. Cr2 G) + oH- (aq) ct- (aq) + CJlol @q)
Step 3. To balance the reduction half Eq. (ii) -
(a) Balanca oidatiot nuntber by addirtg O.N. of Cl decrcases by 1 per Cl aiom
elecoons. Oi,Jation of N is + 5 on L.H.S. whilc it is
+ 2 on R.H.S., therefore, add 3 e - to L.H.S. of Eq.
Total increase =2x5=10
(il). We have, Total decrease =2x- I=- 2
NO, (aq) + 3e- 'No G) ...(,ir) Stcp 3. Fitd out the oidant and the ,edrctana
and splil lhe skeletol Eq. (i) into two half reaaions.
(b) Balance charge by odding H+ ior6. Thc
Here, O.N. of Cl decreases from 0 in Cl, to
total charge on L.H.S. is - 4 while it is zero on
R.H.S., therefore, add 4 H+ to L.H.S. of Eq. (uii). - 1 in Cl-, therefore, Cl2 dcts ss on midotl Frr-
Wc havc, thcr, the O.N. of Cl increises from 0 in Cl, to +5
NOr- (aq) + 4}]+ (oq) + 3 e- + NO G) in ClOr-, therefore, Cl2 acts os a reductant.ln othet
...(viii) words, Cl acts both as an oxidant as well as a
(c) Balance O atoms by addingHrO ntolecules. reductant. Therefore, the two half reactions are :
Since there ue three O-atoms of the L.H.S. of Eq. Reduction half : CL, (il- Cl- (sS) ...(,i)
(viii) but only one on the R.H.S., thcrcfore, add
2 HrO to thc R.H.S. of Eq. (vfri). Wc have, R OidLtion ha[ : Cl2 G) .._ ClOi @il ...(iii)
EE
Step 4.T o bolance the reduction ha{ equation
NOI (aa) + 4H+ (oq) + 3 e-
AR
(ii).
No -+ 2 Hro (/) ...(u) (o) Balance nll aroms other that O ond H.
C
@)
Since there are 2 Cl atoms. On L.H.S. of Eq. (ii)
S
Thus, Eq. (ir) represents the balanccd reduction and only one on the R.H.S., therefore, multiply
IA
Step 4.To bolance the electrons lost in Eq. (vi) c\(oq) '--'' act- (aq) ...(i,)
and gained in Eq (ix), multiply Eq. (ix) by l0 und (b) Balance oxidotion number by adding
Eq. (vi) by i and add. We have, elecfionr. The O.N. of Clin Cl, on L.H.S. of Eq. (iv)
3 As2S3 (s) + 24 H2O 11; .._ 6 a ,6:- 1or.1 is 0 while on the R.H.S. it is -1. Thus each Cl
+9S(s) + 48H+ (qq) + accepts one electron. Since there are two Cl atoms
on the R.H.S., therefore, add.Z e- to L.H.S. of Eq.
l0No3 (aa) +tfiH+ (aq) +30c-- ^Oe-
(iu), we have,
10NoG) +20H2oo
Clz (d + 2e- -----.- zcl- (aq) -.(r)
3 A9S3 (s) + 10 Not (afl + aHro (t) (c) Balance charye. Not needed sinct charge
6 Asoi- (aq) + 9 S (s) + 10 No G) + 8H+ (sq) - on either side of Eq. (v) is balanced. Thus, Eq. (v)
represents the balanced reduction half reaction.
This gives the final balanced redox equation.
Step 5.'Io bolance the oxidttion half equation
. liX.Ar\{PI.lt t).12. In passing chloine gar (iii)
through a concentrated solution of alkali, we get (a) Bdance all atoms othet than O and H,
chloidc and chlorate ions. Obttin balqnced, chemi-
cal equation for tlii rcsction. (NCE.R.r) Since there are 2 Cl atoms on L.H.S. of Eq.
(r'rr) a.nd only one on the R.H.S., therefore, multiply
-Sdu!l.gn. Step l. Wa'l e the skeletsl equationfor
the g,]',cn rcaction ClOr- ion by 2, we have,
Cl, G)+OH- (aq)+cl- (aq)+Cto, (oq)...(i) c\(0 zctot (aq) ."(v,
-
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9122 , Ned Course Chcmistrg !;eil)
(b) Balance oidation number by adding cl2 (9 + tzoH- (aq)
electons. The O.N. of Cl in Cl, on L.H.S. of eq. (vi) zclo, (oq)-+ 6HzO (0 + 10 e- ...(i:)
is zero while in the R.H.S. i.n ClO3-, it is + 5. Thus,
By doing so, H atoms are automatically
each Cl atom loses five clectrons. Since there are balanced, therefore, Eq. (rr) represents the
two Cl atoms on R.H.S., therefore, add 10e- to balanced oxidation half equation.
R.H.S. of Eq. (vi), we have, Step 6. Tb balance the electrons gained in Eq.
70e- (v) and lostin Eq. (ix), mulriply Eq. (v) by 5 and add
Ctz G) aclot (aq) + ...(vr,
-
(c) Balonce charye by adding OH- ions since
to Eq. (ix), we have,
+ lO e- .-.-+ l0Cl-
5Cl, G) (aq)
the reaction occws in the bask medium. Tbe total ct2 @) + 72oH- (aq)
chargc on the R.H.S. of Eq. (vr'i) is 12 and zcro - zclo, - + 6Hro (/)
(aq) + 10 e-
on the R.H.S. Therefore, add 12 OH- ions to the
L.H.S., we have, 6clz @) + lzoH- (oq) """'t
clzB) + taoH- (aq) "'--'.2clq @q) + I:oe' L}Cl- (aq) + 2clot (aq) + 6Hro ({)
...(viii)
(d) Balance O atoms. The R.H.S. of Eq. (vnt)
or 3Cl2 @)+ 6oH- (aq) -""+
contains six O atoms but on the L.H.S., there are 5Cl- (oq) + Clo, (aq) + 3H2o (0
12. Therefore, add 6HrO to the R.H.S., we have, This represents the firral balanced redox
cquation.
R
EE
AR
l. Balance the following equations in acidic medium (Pni) H2S G) + Fc3+ 1a41
by both oxidation number aod ioll electron
C
tants :
(ix) l- (a4 + to; (oID + H+ 1oq1
IA
) @) r- (oS) + 02 G) + H2o (D
(v) CrrO]- @q) + czH'/o (aq)- (rv) cu (.r) + Not (aq) + H+ (aq)._
CF+ 1a4; + czl{41zll,q) Crz+ (oq) + No G) + H2O (r)
(v,) MnO; (oq) + Br- (oq) + (rv) zD (r) + Nol (a4 +H+ @4)-
Mr:2+ 1aq; + Bt2 @q) Zoz' <oq) +N2o E) + H2o (4
(v,i) cu (44)+Not 1*'1- coz+ (oq)+Noz?) (xrr) Sr (aS) + Not (oq) + H+ (4q)
(N.C.E.R.T.) - + H2o
snoS- (a{) +No2 G) (r)
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REDOX BEACTIONS 9123
I\ (t 2MnOi- 1q1 + eU+ @q) + sczHz}4 @q) 2. Balance the follotping equarioos in basic medium by
both cfiidation numbcr and ion eleclron merhods aDd
2ynz+ pqy l l oco2 GI) + 8H2o (r) idcDdry the reductants aDd the crddants.
-
(ri) H2S (aq) + ctzg)+ (0 P (r) + oH- (4s)- PH3 G) + urPOl (a4)
s (r) + 2Cl- (4g) + 2H+ (o1) (N.C.E.R.T.)
(iii) 4MDOa- (a{) + sczHsOH (o{) + 12H+ @q) 0D N2H4 G) + clot (aq)- NO (g) + ct- (aq)
* 4Mn2+ + 5CH3COOH (aq) + l1HzO (0 (Nc.E.R.T.)
(tr) Cl2O7 G) + HzOz@q)*
(iv) Bi(s) + 3No3- (4q) + 6H+ (oq)-
cto; (aq) + o2@) (N.C.E.R.T.)
Bi3+ (4q) + 3No2 G) + 3HzO (I)
(iu) C(OH)a pq) + HzOz(pO-
(v) c;zolt- @q) + 3czH1o (oq) + BH+ @q)
c/.Ol- @q) + H2o (t)
2g1s+ @q) + 3c2H1O2@!t) + 4H2O (r)
- (v) Zo (r)+No3- (4q)- 7n2+ @q+NH[ @4)
(vi) 2MnOo- @q) + loBr- (aq) + ]6H+ @q)
(!r) At (r) + N of (a{) --
2YDz+ @q1 + sBtz@q) + 8H2O (4
- N(OH); (aq) + NH3 G)
(r,r'i) Cu (r) + 2No3- (4q) + 4lg^+ @q)
-
2Fe2+ 1aq1+ s (r) + 2H + (aq)
(r) + snol- (a4) ..-
S
(.r) Bi(OH)3
(ir) 5l- (aq) + tol
N
(r) Bi (r) + 3Not (oq) + 6H+ (aq)- (r) Cr (r) + cto; (oq)
-
BP+ + :NO, 19; + 3H20 (I)
Cr(oH)3 (.r) + ctot (oq)
1ag1
(vii) PbO2 (r) + ct- (aq) + HzO (D + oH- (a{) (v) lt + HNO3
- Fe(No3)2+NH4No3+H2o
Pb(OH)3- @q) + cto- (aq)
- (vi) Sb - HNO3 HrSbO. + NO2 + H2O
(tiii) ZFu(OH)2 @q) + u2o7 @9)
- (vii) Hg + -
IINOr- Hg"(NO3)z + NO + I-I2O
t"
l.\nr. (i) SnO2 + 2C+ Sn + 2CO
(&) 2 B(oH)3 (r) + 3 snol- ,*, l"to" (ii) Fe3Oa + 4C- 3Fe + 4CO
2 Bi (r) + 3 sno3- @q) + 3 H2o (l) (iii) 12+10 HNO3 ._ 2 HIO3+ 10 NO2+4 H2O
(x) 2 Cr (r) + 3 cto; (aq) + 3 H2O * (iv) 6 FeSOa +2HNO, + 3 H2SOa
2 C(OH)3 ('i) + 3 ctot (arl)l 3 Fe2(SOa)3 + 2NO + 4 H2O
3. BalaDce the following redox reactions : (v) 4 Fe + 10 HNO3
(i) SnO2 + C+ Sn + CO -
4 Fe(NO3)2 + NHaNO3 + 3 H2O
(ii) F%Oa + C- Fe + CO (vi) sb + 5 HNo3- Hjsbo4+5 No,+Hzo
(iii) I, + HNO3 HIO, + NOz + H2O (rii)6Hg+8HNO......-
- + H2SOa
(iv) FeSOn + HNO, .._ 3H82(NO3)2+2No+4H2Ol
Fer(Soa)3+No+I'I.o
reactions. 6x(56+32+16x4)
S
tiply oxidant of Eq, (i) i.e. MnOo- by (5-+r) and (i) Oidation of fenous salts :
reductant of Eq. (r'!) ie. An+ by 5 and equate, we 6Fe2+ + Crro|- + 14 H+ -----'
haic, 2CF+ + 6Fe3+ + 7H2O
(5-n)MnOo-=54"+
A'+ (ii) Oxidation of Mohr's salt :
i.e., (5-+l) moles of MnOa- will oxidise =
Mohr's salt is a double salt of (NHn)rSOo and
5 moles
or 1.61 x 10-3 moles of MnO.- will oxidisc FeSOo r'.e. (NH1),SO1.FeSO1.6HrO. Out of thesc
two salts, CrrO|- oxidises FeSOo to Fer(SOn), as
5 per the equation shorm under oxidation of ferrous
=Fi;" 1 6 x l0-3moles ...(iri)
salts.
But the number of moles of An+ actually 3, Ceric sulphate tttmflons. In these titra-
oxidised tioDs, the reducing agents such as Fe2+ salts, Cu+
= 2.8 x 10-3 moles
...(ir) salts, nitrites, arsenites, oxalates etc, are directly
Equating the values of Eq. (rrr) and (iv), we titrated against ceric sulphate, Ce(SOo), as the
have, oxidising agent. For ercample,
5 x t.61 x 1o-3 = 2.68 x 10-3 (i\ Oidation of fenour salts :
5-n
=
Fe2+ + Ce.+-aFe3+ + CC+
or 5 x 1.61 -(5-n)x2.68 Fcrousion C€ric ion FeEic ion Ccrcus ion
or 2.68n = 5 (Z'68 - l'67) (r) Oxidation of aresinites (AsO3-) to ar-
-5xl.Ul=5.35 senatcs (AsO!-).
or n =ra=5'35
z R A"o3- + 2Ce'++Hzo-
EE
9,122. Det€rmlnotlotr of stolchlomettf uslng Ars.nitc ion Ccric ion
AR
Redox tltratlons. These titrations involve the reac- Asol- + cd+ +2H+
ticn between cxidising and reducing agents in
C
categories :
IIT
Mol. of IQCr2OT
electrons gained or lost. Thus, rrre equivalcnl weighl
IA
=
s5 lre = zt't =2+r9 =n
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REDOX HEACTIONS
-
H2SnO3+4NO2+2H2O
1v;
Aszsr + H+ + Nof
C
NO+HrO+AsOl-+SOn2-
N
3AgNO3+NO+2HzO
[ turs.(i) M (ii) M (iri) W2 (it) Wta O) l\AzEl
IA
g1 + zn + lo lxo:
IIT
1a,4
2. Determine the equivalent weighl ofthe underlined
specie,s/compounds in the following equatioDs : zl
-
Zn (No3)2 + NHaNo3 + 3 H2o
(4) s2o3- + 5 H2o + 4ch- I \n\ (a) 14; (r) HS- = t.25, HSOr- = 40.5;
2SO1-+8Cl-+10H+ (c) Mho2 - 43 S, KclOs= 20.4 ' <d) 2r'3
(iv) Calculate the total chaDge in O.N. of one Total increase iD O.N. = 2 + t2 = t4
molecule of FeS2 Hence, Eq. wt. = M/14
FeSz=Fe2++252- (y) Calculate the rotal change in O.N. of one
molecule of AtS3
2+ O.N. incrcsses +3
2Fe FerO, AhSr=2As3+ +352-
WZxl=2
+4 _. O.N. incrca6es +5 -
2S
O.N. incrcascs
2 SO2
2 Asr. 2 AsOi-
W2x6,12 by2x2=4
-+
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9128 i t " ,, . Nett Coursc Chemistrglftffi
= 712/8 = 14
2x13
=-4_=16.s
-2 ._ +2 2-
(6) (0 2 [H s]- s2 03 o(0rot-r-
Tbtal change in O.N. ofS Total change in O.N. of I=+5- (- t) = 6
=2x(+2)- (2 x -2)=8 .. Eq. *r. of lor- = Moli wr 12? 48
qi' 62 = -+ - 17 .
s
,.. Eo.wt.of
,8 Hs- - 2 x Mol +4 +6
(i0 Hsoi sol-
=2133=r.zs Tbtal change- iD O.N. of HSOJ = +6-4=z
+4+2-
(ii) 2 HSO3- 52 Ol-
.. Eq. Et. of Hso3- - M'l *t - $ = lo .s
- +4 R +2
Ibtalchange O.N. ofs - 2 x4 -2x2=4 *
EE
iD
G) MnO2 MnCl2
2 x l\'!ol wt M'l*t =f
-
AR
=--?-=lo s
(r) (l) sn ..- lt2sDo3
+4
S
+4 +6
N
- O.N. of Mn = 6
'Iblal change in
- 4=2 +5
IIT
+4
.. Eq.wt.of Mno2= Mo! wt (i0 HNo3 No2
=55;32 =a3.s -
Eq.wt. = 1r4q1.wt. = 1 + 14 + 4E = 63
+5 -1
(it) KCro3 * KCr +5 +2
(i) HNO, p6
Tbtalchange in O.N. of CI = 5 - (- t) = 6
-
Eq. wr. = 11461.1y1.;3 = 638 = 2l
.. Eq.wt.of Kcloi = Moliwl - 12? 5
- 20.a +5
6o 0) HNo3 -*
-3
0+5 [NH4]+
(d) Clz Tbtalchange in O.N. ofN - 5 - (- 3) = 8
-2NaClO3
Tbtalchange in O.N. ofcl = 2 x 5 .. Eq. wt. = Mol. 1l1.E = 63/8 = 7.8A
- O = r0
,based(i)upon
Normallty. equatlon. This equation is .'. V, cm3 of N, KMnOn contains KMnC)o
the law of chemical equivalints which
N.
states that substances react in the ratio of their , V, gram equivalents
equivalent weights. To derive this equation, let us = 1000
consider the volumetric titration between acidified and V, cm3 of NrFeSOo contain FeSOo
KMnOo and FeSOn solutions. Let N, and N, be the
N,
normalities of KMnOo and FeSOo solutions respec-
1000
= , V, gram equivalents
tively. Suppose V, cm3 of N, KMnOo solution react Since substances react in ratio of their gram
completely with V2 cm3 of FeSOo solution. equivalent weights, therefore,
tNormalityis dcfined as thc number of gmm eq u i!"lcn: 1', cigh ts of a substancc dissoh'ed pcr litrc of the sotulion.
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REDOX BEACTIONS
9/29
NrVt/1000 = NzVz/1000 coefficients, we can derive the molarity equation.
Consider for example, the vol,rmetric titrat'ion be-
or N,xV,=N2xV2 trveen KMnOo and FeSOo solutions. The balanced
This is called normality equation. With the chemical equation for this reaction is
help of this equation, we can easily determine the 2KMnO. * .f SH2SOn....-r
10FeSO.
normality (N,) of anyunknovm solution if we know IQSO. + 2MnSOo + 5Fe(SO1)3 + 8H2O
thc yolume (Vr) of this solution which rcacts com-
pletely with another solution of normality (Nr) and Suppose V, cm3 of Ml fUnO. solution rea9
volume (Vr). Having determined be normality of completely with V2 cm3 of M, FeSO. solution.
the desired solution, its strength can then be calcu- .'. V, cm3 of M, KMnOn contains KMnOn
lated by the relation,
M.
Strength = NormaLity of the solution =mxV,moles
x Eq. wt. of the solute and V, cm3 of M, FeSOa cortain FeSOa
e days, morality cquation the balanced chemical equation (l). If we now repre-
sent these stoichiometric coellicients by n, ani n,
C
Mrvr M2v2
_
IA
equation for a redox reaction, This is called morallty cquation and can be
oA+b8.......>cC+dD used to determine any unknown quantity if the
Here A and B are the reactants while C and otber tbree quantities are koown.
D are the products. The coefficients a, b, c .and d Jn gcneral for any rolumctric titration inrohing
are called stolchlometric coefiicients. These coef- rcaction be turcen A and B, the molarity equation is
"
ficients indicate the number of moles of the reac- Molarity of sol. A x Vol. ofsol.A
No. of moles ofA in balanced Eq.
_ Molaritv of sol. B x Vol. of sol. B
- No. of .otoEE-iiT iiEZEll
:tolulion.
Step 2. To determine the moloity of SQ- ion
- Molaritv=I&!E!L,
*--1ffi
.
Let M, be the molarity of SOI- ions in acid =1,f lN = 0., t
t44" 19
rain water. Applying molarity equation, Step 3. To calculate lhe volume of 0 01 M
R
M,V.
EE
M.V. KMIO. solution
---= (So3-) = ---:--1 (Mno;)
AR
Mr x 25 M.V, M,V^
x 0.02
= ,'2' '(KMno,)
S
35
or5=z ,j tn"c'o')
N
IA
i
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Netu CouYse Che i stru
9132
KMno4 solution in acidic medium' What is the to ICI. Find out the lalue of V [ .\us. 20 cm3l
pcrcrntage purity of the samPle of H2O2 ? 1r. Both cr2ol- (4q) and Mno4- (44) csn bc uscd to
[ \ns t57o] titrate Fe2+ (4q). lf in a given titration, z'50 cm3
10. 16.6 g was dissolved iD
of0 1 M Crzol- were used, then what volume of
wate; uPto one litre' V
cm3 of with 20 cm3 of2 0. 1 M MnO; solution lvould haYe been used for
M HCI quired l0 cm3 of the same titration ? I At's. 29.4 cm3l
FORDIFFICULT r2R.O
20 I
l. Balanced equation for the redo'x reaction is: 15 12
truror) - tn"so,)
2KMnOa + 5 (COOH), + 3 HrSOo-
to i.,M
i rcroi-) =
S
= 1fi)0 cm3
or
N
Mr =0 02M
. 0 of KMnOI is Present in solu(ioD
IA
. 0'12 mole
qol- = e€
IIT
coi.j'iD.
6. Balanccd chemical equatioD is:
= 158 + l8.r
ZK^CrzO7 + 3Sn+28HCt .. Amouflt of Na2S2O3 .rH2O prescnt per litre
2(: x39+2 x5:+7x l{,) 3x356.t
116 7 -
=2x294 - g - (1s8 + 18.r) x 0.Or 8
=5E8s But the adual amount dissotved 2.48 g
4KCl + 4 C[CI3 + 3 Sncta + l4H2O =
EquatiDg these values, we have,
Now 356.1 g Sn react wi r IqCr2OT = 588t (15t + 18r) xo.O1 =2.48 orr=s
9. No. of moles ofKMDO4 prcsent in 20 mlof0.1 M
.. l gSn wil reacr with IqGrO? = ;:qig
KMnO{ solurion = -?9- " 9.1 = 2 x l0-3
= I .6519
Eq. *t. orK2cr2o7 = t'of* =?=0, The balaoced equaron for the redox reaction is :
2KMnOa+5H2O2+3H2SO1--
Decinormal K2C[2O7 solutio[ means l00O cm3
solurior-r coritaiiis 1.9 g y\Crzol, i.e. 1.9 g K2SOa + 2MoSOa + 8 H2O + 5 02
From the equation,
IqCr2O? are present iD l00O cm3 solution
2 moles of KMnO4
.. l = 5 moles of H2O2
65t I K2CtzO:. wil be present in
1000
.. 2 x 7O-3 moles of KMDO4 will react with
{f x l 65l cnrr = 336.9 crn3
arOr=|xz xro-3=5 x to-3 rroles
7. No. of mittimoles of IqCrzOT presenr in 24 cnt3 of
R
Mol. w1. of H2O2 = 34
EE
0 5 Msolution = 24 x 0.5 = t2
The balanccd chemicalequation for rhe redox reac_ .. Amount ofH2O2 actually preseot
AR
tion is :
=34x5xtO-3=O.l7g
C
-
IA
r cr"(So4)j + 43 H2O 10. The ctremical equation for the redox reaction is
IIT
:
Fiom rhe balaDced equation,
IO3- +2I- +6HCt+3ICt +3Cl- +3H2O
6 moles Mohr's satt are oddised by IqCr2OT
= 2 millimolcs $Jror=!i!1,oo,,
t. The balaDced equatioD for the redox reactioo is : or V=20cm3
2 Na2S2OJ + Iz ...-,Na2SaO6+?NaI 11. Suppose V, cm3 of M, Fe2+ is ritrated agaiost
Lct thc nlolarity of NES2O3 .x H2O solution Ml
= 2 50 cm3 o.r M Crrol- and V, cm3 of 0.1 M
Applying molarity equatioD to rhe above redox
rcaction, we have, Mn04- solutions, then,
M, x20
_--_ ('! .2u3) = (I2)
?1{-!11c,,q-) -',,v, ir",*y
i (,
.. Mt=oolM Vr x0.l M^V-
cnd ---- (MnOo-) = -i-:1Fe2+)
Mol. wt. of Na2S2O3 .-rH2O ...0.r)
- 2 x 23 + 2 x 32 + 3 x 16 +.r x 18
Equating (i) ard (ii), Vr = 29.4 cm3
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coll. Thus,
cell
,4n electrochemical celt or simply a chemlcal
R
EE
AR
C
bridge.
S
no
reaction takes place in either ofthe beakers and
IA
IIT
POROUS POT
soL.'
zrNc Roo
ZnSO!
soL.
...(O
etecuTc cunent will not occur as e>rplained below '
The overall reaction taking place in rwo :
C
Zn (s) + C\2+ (aq).-...- Z.*+ (a4) + Cu (s) copper wire, the flow of electrons from zinc to
N
IA
IIT
migrate from CuSOo solution to the ZnSO. solu- As Zn2+- ions are produced near tbe zinc rod,
tion. an equal number of SO!- ions will mou"
fronr i#
. 9.132. Salt bridge and its funcflons. The two
main functions of the salt bridge are as follows :
. .(i) It a[ows the movement of ions from one
solutron lo the other without mixing of
the two
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Net4 Coarse Chemlstrglffi
om the negativcPole
a result. the solutions in the two beakers remain circuit However'
electically neutral and lhus allow lhe electic
cwrent to nal
;; suid ro flow itr' tltc
to llow.
9.133. Salient featurcs ofan Electrochemical
cett. Som" important foatures of an electrochemi-
cal ccll are sumarized below :
(i) Thc zinc ro occurs
the anode
which
is caliid
iieietluction take" d"'
current falls with the passage of time'
(ir) As a result of rcdox rcaction' lhe weight
,'r .Jn.i"i rod increuscs whilc thut uf zinc roJ
J..r.'ri.t rr,lI' g"in and loss in wcights oIthc nrcti'l
.,,,t. i. ln ttt. raio of thcir equiYalcnt wcights For
example,
l-oss in wcil,ht ol Tinc rod E(l' \\4 o[ Ztr
GffiGshGf .qrP.**t - Eq 'r1 of cu
-3250
31.75
Somc imporatnt gcneralizi'tiorts atrout an
ctrochemical'cell maybc summed up aslollows
:
ele
R occurs at lhe anodc whilc reduction
EE
Oxidation
-oi..ru's at the cathode
AR
(v) The two half reactions always take place urrent lows from calhode lo
N
tokc
simulianeously, i.e., ha[ cell retctions cannot
IA
unode.
m
Chtmical energ ol lhe redox rtsclion occutnng
IIT
9.13.4.ReprtsenlatlonofanElectrochemical flE
Cell
An electrochemical cell is ropresented in a electode potantial
manner as illustrated below for the Daniell cell :
to lorm
-
IA
In a similar manner Cu AgNO, cell may be the electrons thus released accumulate on the rod
IIT
9.14.1. Delinitlon.
It has been discused above that each
electrochemical cell consists of two electrodes or
half cells. Each electrode, in turn, consists of a
metal dipped in the solution ofits own ions. At ore
of these electrodes, oxidation occurs while at the
other, reduction takes place. In other words, one
oo
OXIDATIONTENOENCY REDUCTIONTENDENCY
_'The_activiticsofpurEsolidsandliquidsor€lakclasunityandindilutcaqucoussolutions,thcactivityofagiv.nsolutionis
nearly equal to its ftolarity. For gaseous spccies, thc activityis nearlyequal to its pafiisl prcssurc cxprcsscd in bi. Thus at 1 bar
pressure, thc activity of thc (ascous species is ncarlyone.
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REDOX REACTIONS 9/39
To determine the electrode potential of any electrode to the hydrogen elcctrode. Since oxida-
electrode, a cell is set up using this electrode as ons tion occurs at thc zinc clectrode, therefore, the
of the electrodes and the second slectrodu is the standard electrode potcntialfor Z*+ /Znhalf cell
standard hydrogen electrode. The EMF of the cell is - 0.76 volt.
is measured. As the EMF of the cell is thc dif-
The two halfreactions taking place in this cell
ference in the electrode potentials of the two half
are :
cells and since the eloctrode potential of the staod-
ard hydrogen electrode is taken to be zero, there- Zn(s) Zna+ (aq) + Zc- (oxidation)
fore the EMF of such a cell will directly give the -> +
zE+(aq) 2c---.-..-,}{,6) (reduction)
electrode poteotial of the cell under investigation. (u) Delemrlnation of tbc standard electrode
The direction of flow of current further indi potential of Cul +,/Cu electrode. A cell comprising
at of standard hydrogen elcctrode on the let and
to copper electrode , ,'.e., Cu rod immersed in
lM CUSO. solution on the right is set up as shown
vent o.iti;" in Fig. 9.7.
sign oxida-
tion gation Here, the EMFof the cell comcs out to be 0.34
with volt and the direction of flow of electrons is from
the hydrogen electrode to the copper electrode r'.e.
The determination ofelectrode potential may
reduction occurs at the copper electrode. Since
be further illustrated with the help ofihe following
reduclion occurs at the coppcr electrode, there-
two simple examples :
fore, the staodard electrode potential for Cu2+/Cu
(i)Determination of slandard electrode half cell is + 0-14.
potential of Zn2+ / Za ele&rode. A cell compris- R
EE
The two half reactioru taking ptace in this cell
ing of zinc electrode, i.e-, Zn rod immersed in
:ue :
1 M ZnSOn solution is on the left and thc standard
AR
and the direction of flow of electrons is from zinc potential for non- nrelals which givc ncgative ioDs
IIT
VOLTMETER
SALT BRIDGE
H2 GAS AT
18AR
PR E SSUR E
,I
M HCI
sot
Pt FO'L
H. GAS AT
'tB,tn
PRESSURE
lMHCI
soL.
R FOIL
tion of ch.loride ions. The half reaction for such an potentiols. If, however, reactions are written in the
S
Further, using standard hydrogen reaction is just the reverse of oxidation half reac-
electrode, we can determine the electrode poten- tion, the oxidation potential of any electrode is
tial for metal ions involving variable oxidation obtained from the reduction potential just by
states. For example, the electrode potentialfor the sfinnging the sign. For example, the Jran dard reduc-
system, Fe3+(a4) /Fe2+(aq) is obtained bymeasur- tion potential of the electrode Znz+ /Zt (aq) for the
ing the EMF of the cell given below using Pt as the reaction,
inert electrodes,
Zn2+ (aq) + 2z- Zn(s) is - 0.76 \
----.-----,
Pt lHrG) lH3O+(aq) llFe3+ (aq) ;Fez+ (aq)l Pt.
then the standsrd oxidation potentiol of lhe
From the above discussion, it follows that a elecftode Z,a./Zrl+ (aq) for the reaction,
metal in contact with its own ions constitutes a half
cell and if we join two half cells together yia a salt
Zn(s)- Z*+ (aq) + k- is + 0.76Y.
bridge, we get an electrochemical cell. For ex- According to the latest convention adoptedby
ample, Daniell cell can be made by joinitrg the two IUPAC, the terms standard oxidation electrode
half cells i.e., Zn (s)l Znz+ (aq) and Cu (s)/Cu2+ potential and standard reduction electrode poten-
(aq) by a IQSO. salt bridge or tho two half cells are tial are not used but only the term standard
electrode potential is used and the half cell reac-
separated by a porous pot. tioos are always written as reduction reactio[s.
'l: 1 ,r,c,r Furthcr,
Standard electrode potential is given a posl.
lhe stalrdard electfode oolentrals ol a ttve sl8,r.if rcduction occtt* otthat eleclrode L''rt' lhe
--- - bJeln;;;;#.;
larse number of erect.odes have --'...--*:----*
reference -':"-:;'
stq,tdard hydrosen electrode and is giverr a negative
usinc standard hvdroscn electrode as the !|:.4
srgn u o*qalron occurs 4I Ine etectroae w'iL tne
elecirode, for rihich the electrode potentiat has
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HEDOX REACTIONS 9141
standa hydmgen electode. Futhq the mognitude table, the reducing agents are written in decreasing
ol lhe slandard elecEode potential is a measure oI the order of their strength i.e., the tendency of the
tendency of the haff reaclion to occur in the torward oxidation half reaction goes on decreasing as we
direcion i.e., in lhe direction of reduction. move from top to bottom. Such a llst of reducing
The standard electrode pot€ntials of a num- agents amnged in deoeasing order of thei strength
ber of electrodes at 1 M concentration of the dis- is cdlled the actiity or €lectromotlve or
solved ions at 298 K are given in Thble 9.1. In this electrochemlcal serles.
Electrode Reoction
pq1 CrG) 74
-0
Fez+ (aq) + 2e- Fc(r) ---0.40
C
S
PbSOa(r)
IIT
e-
Fe3+ 1oq'; + F"'* (oq) +O7'l
tt$+ @q) + zc- 2Hs(I) + 0.79
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9142 Pradeep's
TABLE 9.1. Contd.-.-..
f. To comparr th€ reducing and oxldlslng reducing power decreases in the opposite, i.e.,
Li >K>Na.
S
potentiol is great$ thon zero, then re&tced lorm is Besides the above applicationq electrochemi-
IA
more stoble than hydrogen gas. Similarly if the smnd- cal cells are exten"sively used for determining the
IIT
atd elecfiode potential is negative, then hy&ogen gos activity coefFrcient of electrolytes, pH of solutions,
is ntore stoble llrun llv rcduced Iorm oI species. ln solubility product and for potentiometric titrations.
other words, a negative Eo means that the redox Electrode potentials can also be used to determine
couple is q stronger rcducing agenl than the H+ /H2 the stability of inorganic and organic species.
couple ond a positive E" means thst lhe .redu couple From the above discussion, it folloux that a
is u wcaker reducing agenl lhan lhe H' /H2 couplc.
rnetal which lies higher up in the series is a better
The standard electrode potential of fluorioe is the reducingagent in the aqueous solution thanthe one
maximum in the Table 9.1, therefrrre, F, is the which liesbelowit. Ttrs, whereas zinc can displace
strongest oxidising agent and F- ion is a very poor tin, lead, copper and other metals lying below it
reducing agent. Since the standard electrode from the aqueous solutions of their salts but copper
potentials of halogens decreases in the order cannot displace lead, tin, zinc and other metals
F2 > Cl2 > Br, > Ir, therefore, their oxidising
lfng above it from the aqueous solutions of their
power decreases in the same order, i.e., salts. Similary, copper can displace silver from its
F2 > Clz > Br, > [r. Conversely, the standard
salts but the reverse does not happen
electrode poteutials for halide ions decreases in the 2. To prodlct wh€ther a metal wlll liberate
order : I- (- 0.53 V) > Br- (- r'08 V) hydrogen from the aqu€ous solutions of acids or
Cl- (- 1 36 V) > F- (- 2'87 V), therefore, not. AII metals with negative electrode potentials
reducing powers of the halides decrcases in the
are stronger reducing agents than hydrogen and
same order, i.e., I- > Br- > Cl- > F- hcncc would liberate hydrogen from the aqueous
Among alkali motlls, l.i (- 3 05 V) has the solutitrns of acids. Conversely, all metals with posi-
lowest while Li+ ( r' 3 0-5 V) has the higlrcst tivc values of electrode potentials ore tt."U"t
4
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FIEDOX REACTIONS 9143
reducing agents than hydrogen and hence will not will libcrate hydrogcn but metals like Cu, Hg Ag
liberate hydrogen from the the aqueous solutions etc. do not liberatc hydrogen from the aquoorls
of acids. Thus, metals like Mg, Al, Zn, Fe, Sn etc. solutions of acids.
f)\,\lll'l,I.l t).19. The standatd elecffode Since E (1.50 V) for Au3+/Au is higher than
potentiql corresponding to the
r€qctiott
tnat n+lln, (0.0 v), therefore, Au3+ can be
Au3+ (aq)+3 e-'-"'-Au (s) Ls I '50 V Predict iI Bold
can be dissolved in lM HCI solution and on passing more easi.lyreducedthan H+ ions. This implias that
hydrogen gas through gold salt solutio4 metallic gold Au3+ ions can be reduced to metallic gold by H,
willbe precipitqted or not. (N.C.E.R.T,)
gas but H+ ions cannot oxidise metallic gold to
Solution. Consider the half reactions, Au3+ ions. In other words, metallic gold does not
zIJ' (aq) + 2e- .--"'+ H, (3) ; E" : 0'0 V ilissolve in 1 M HCl. lnstead H, gas caa rcduce gold
PO:R ,EJE;
2. With the help oftablo 9.1 select lhe reducing ageIlt
can oJddisc oxidise which can reducethe followingions totheir metallic
(a) Ct- (oq)ro Ct2@) staie (a) Ag+ (aq), (D N+ @q) and
R
EE
(c) Ni2+ (ry). (N.C.E.R.T.)
(6) Fe (.r) to Fe2+ (aq) and
IdeDtiry the strongest and weakest reducing aSents
AR
(c) l- (oq) Lo 12@q) (N.C.E.R.T.) from ihe following metals : Zn, Cu, Ag, Na, Sn.
C
(N.C.E.R.T,)
S
N
IA
1. ejl E higher than Cl-./Cl2 2'1a.1 Alt mctals having E" lower lhan Ag+/Ag
IIT
9.16. EMF ol an Eleclrochemical Cell ri'.'r':':r',+.;e,.+::ii:ri Ws know that an electrochemical c.ell consists
of two half cells, i.c., clcctrodes. C)ne of lhese
It is a well known tact that whenever a cur- electrodes ltust havc a higher electrode potential
rent flows through two points, a potential dif- (higher tendcncy to lose electrons) than the othcr
ference is said to exist between them.The potential electrods. A.s u result of this potential difference,
difference generated by a cell when the circuit the electrons flow t'rom thc electrode at a higher
draws no current (under conditions of zcro potcntial to thc elsctrodc at a lorver potentiul, i.e.,
electron flow) is called electromotiYe force (EMF) irom nerlativc electrodc to lsss nsgative or positive
or the cell potentlal.
r\
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9144
electrode or from less positive elecl.rode to more / lrx-{luI'f,li 9.2{t. A cell is prcpared by dipping
positive electrode. However, current flow is in a a chromium rod in I M Crr(SO.), solution and an
direction opposite to the electron flow. Thus, iron rod in I M FeSO , solution. fie standard reduc-
EMF of a cell mry be tion potentiqls of chromium and iron electrodes are
the elocltoilc pstentlols -0.75 V and -0 45 V respectively.
efl is @ wndincc.wryrt thmvdt tlrc sirait. (q) What wi be the cell ,caction ?
The standard EMF of the cell (E may be (b) Whqt will be the standard EMF of the cell ?
".r)
obtained by subtracting the standard electrode (c) lhich electrode will act qs anode ?
potential of the anode from that of the cathode, i.e., (d) l4hich electrode will acl as cathode ?
Solution. The two half cell reduction equa-
tionsf, I
Fez+ (oq) + 2 e- ' Fe (r) :
E"=-0.45v...(r)
or Eo.",, = Eocathode - Eo"nod" ...(rr) CF+ (oq) + 3 e-'--, Cr (r) ;
Further by convention, the anode is placed on E.=_0.75V...(rr)
the left and cathode is placed on the right while Since Cf +/Cr electrode has lower reduction
representing an electrochemical cell, therefore, the potential, therefore, it acts as the anode whlle
EMF of the cell is given by the e)eression Fe2+/Fe electrode with higher electrode potential
E : Eop - Eo1 "'("') acts as the cathode .
""n
where E\ and Eo" refer to the standard To equalise the number of electrons, multiply
R
Eq. (i) by 3 and Eq. (ii) by 2. But do not multiply
EE
electrode potentials of the cathode and anode
respectively. their E values. Thus,
AR
(i) Wite reduction equations Iot both lhe zCF+ (aq) + 6d- ,2Cr (s);
N
To obtain the equation for the cell reaction, Pb (s) + 2 Ag+ (aq)-------
multiply Eq. (,i) with 2 and subtract from Eq. (i),
from Eq. (di), we have, Pbz+ (oq) + 2 Ag (s) ;
E"..rr = +0 80- (-0 13) = a 6 93Y
(v) Ni (.r) | Ni2+ 1aq; 1 I As+ (aq) | As (r); nickel electrode. Btrz+, m = _{.25 voltl
I
Eccn = + 0 80 - (- O 44) = 1 1 24Y 6. The e.m.t (E) ofthe fo ot ing cells are
C
S
(yi) Cu (.r) | ctz+ 1oq1 I I As+ (aq) | As (r) fu I A8+ (1 M; ll Cu2+ (l M) Cu;
N
;
E ccrr = + o 8o - (- 0 34; = 16 46Y. E'=J) 46V
IA
IIT
@ l,lKAltPl-ti 9.22. Predict whether zinc and sil- Thus the EMFof the supposed cell comes out
eer reuct with 1 M sulphuic acid to give ont hydrogen to be negative. Hence this reaction docs not take
or not. Givert thal the stqndqrd potentials of zinc ond place.
silver are - 0.76volt and t 0.80 volt respectively' /
lix.\l\l ['t,la 9.2-1. Can a solution of I M copper
(q) To predict rcaction of zittc with sulphate be stored in a vessel made of nickel nwtql ?
sulltlruic acid : Given that E.y; ,y12+ :
+ 0.25 volt,
If Zn reacts, the following reaction should Ecu ,crr*: -0.34 volt.
take place ot Is itpossible to store copper sulphate solution
Zn * HrSOa ...* ZnSOr*Hz in a nickel iessel ? (N.C'E'R'T')
i.e., Zn*Z}l+- Znz+ + H, In this Problem, we want to see
whether the following reaction takes place or not
By convention, the cell will be represented as R Ni+ cuso4 + Niso4+cu
EE
Ztl Z*+ llH+ lHz +
i.e. Ni2+ Cu
AR
Ni + Cu2+
Stanrlard EMF of the cell ----
8y convention, the cellmay be represented as
C
,P,-,RAC-TICIE- '
3. Is it safe ro stir I M AgNO3 solutioo with a copFr
lowing metals :
(i) copper (n) tead (ir'i) iron
sPoon? GiirD E'Ag+AS
= o.Eorolt E Cu2+
,
Given E Crr2+ Cu = 0.34 volt ; E.pb2+ pb =--O.34 \Dl!. Frplain Not
rr .
. 4. Can we use a copper vcssel to store
,
I M A8NO3
= --{.13 vok ; and E"Fc2+ Fc = -{1.,t4 votr
, solutio, ? ciwn thal Eocu2+/cu
= +0.34 V
t (r) No (rr) yes Gii) yesl
and Ehs+/As = + 0.80 V
2. Cao a solution of I M ZnSO4 be stored iD a vess€l l.rns Nol
5. Why bluerotour of copper sulphsic lolutbn gcB
Dade of copper ? GiventbatEzl
,h?+ = + 0.76 discharged wheD zioc rod b dippcd in it ?
volt, aod EoCu2+ 0.34 volt
, Cu = (Giveo E"o,2+/ot 0.34 V and
=
I Yesl
Y7y7nz+ = 0.76 1r)
Q. I. Whst rrc the ttroJdmum oDd Dhlm![ qrldotlon ruD]6 olN, S snd Cl ?
Ars (i) The high*t qidsti, numbcf (o.N.) of N b
+5 since it ha frrrc erec'troos in the larcncc rrrcl (2 ,2 2p3)
and it! mlnimum o.N. b -3 lrince it cari accept thrce
conngatim.
chctrom to aquirc the ncarEst
'oorE
i;'g* afi"i
R
(lir-simihrt' thc highcst o.N. of s b +6 sinca it has sk crcctron! in the var€ncc
EE
!he[ (3 ,2 3 pi ano iu ninimum
o'N. h -2 slnce it nc€dr tx.o morc etcdrq'' ro acauirc the nearcsi incn gas
1ar; connguration.
AR
to
Q2 "t.rf-nrcrd "cqr;c
Nrtrrc scrd rcts orry o6 s! odd."rrg sgc''t whirG nl'o* octs bott os otr o drfit o!
S
ogcnt VYhy ?
rs r rcduchg
N
'crr
Ans (i) HNO, : Oxidarion numb€r of N is HNO,
IA
= aJ
M imum Gidation numbcr of N = + 5
IIT
-3 +l -2 +4 +2 +4
(b) c, H; oi @q1 + z H + (d4) + Mn oz (r) .-
MD (aq) + 2 co2 G) + 2 H2o (0
O.N. of C increas€s from - 3 in qH2O4 to +4 in Co2 aDd lhat of Mn dccreases ftom +4 in MoO2 to +2 in
Mn2+, therefore, Mz O2acls 4, lhe oxidonl while CzHzo 4 acls at lhe rcduclani
o +2 2- +2'5 2-
G1lrlaq1 + z s, o3@q1 zt- (dq) + s. o6@q)
- of S increases from +2 in S2O3- to +2 5 in
Here, O.N. of I decreases from 0 in 12 to - I in I- aDd that
s4o? -, therefore, 12 octs qi ,he oxidsnl tehile SrO!- acu as the reductont'
o-1 -1 o
(d) clz?) + 2 Br- (c'q) 2cl- (oq) + Btz@q)
-
Hereo.N.ofcl2decreasesfrom0inclzto-1incl-ionwhilelhatofBrincreasesftom-]inBr-ionto0
in Br2, therefore, Cr2 acts 4t the Nidait while Br- ion ocls at lhe rcduc'anl
(,),5 The electrode Pot.Dtlol of four metsllic etemenk (A, B, CondD) sr.e + 0't0' -'0 76' +0 12 8rld +0 34 V
lo$Er is the
Ans. R
EE
in the sane
AR
order : B, C, D A.
q n ir ria n"r"* added to a solutlon contninlng Br- ohd I- lons what reactlon wlll occur lt
C
Ans. Since E of Br, is hiSher than that of 12, therefore, Br2-has a hiSher
IA
c,nverscly,I.ionhasahighertendeDcytoloseelectroosthanBr-ion.Therefore,tbefollowingreactionwill
IIT
occut:
zl- 4 12+ 2e-
Brr+2e--2Br-
2l'+Bt2-l2+2Br-
In other wordt I- ion will be oxidised lo I ,white Br, will be re&rced m Br- ions'
Ans. (i) We caonot Placr CuSO4 solutioD in a zioc vessel, ii the followiog redox reaction occurs :
CARRYING 1 MARK
Q.1. Dellne oxidaalon srd Fducdon i]r tcr[rs ofelcctron&
ADs Odda ion i[rtolves gain ofelectrons.
Q. 2, What e enuple_
Ars Oxida e called rcdcxoreasions' Mg + F2 + M82+ (F-L'
e. 3. Derire ox
Ars. oxidisiDg educiDg ageob are electron donors.
Q. 4. Ivhat is I
Ars. Refer to the tcxt on p6ge 968.
Q. 5. The stardard elccEode potetrtials of c lev trleaals are giveD belov : R
EE
Al (-f .669, Cu(+O.gV), U(-3.0s9, Ag (+ 0.sov) oDd Ztl ({.76V),
AR
\f,hlch of tbe$e wr[ behrve as the strotrgcst oxrdisrrg sgetrt snd phich aa the
Btrorgcat Fducrtrg ogetrt ?
Ans. Li is the slrongest reducirg ageDl white Ag+is ttre srr6ng-cst qidiSns a;enr.
C
Q. 6. Itr the reoctlon, MrO, + 4HCl + MnCl2 + Cl;+ 2H2O w;k; spccte6ls oxlsted ?
S
N
A CARRYING 2 OT 3 MARKS
in each case'
Scc.9.l. Explain the terms : oxidation and rcduction iD terms ofelectrons' Give oDe examPle
to 9.-1.
ageDts according to the elect ronic concept Givoone
I)efine the terrns: oxidising agent and reducing
example in each case.
3. Comment upon thc statement : oxidation and reduction reactioos 8o side by side'
reactioo ? Give one
Scc.9.4. 4. Wtrut O" yo,i ,o,f"r.tnad by the torrDs : direct redox reactioD aDd indirect redox
to 9.6. example in each case.
to illustrate rour ansrrer.
5. Frrlain o<idatir:o_reduction readiom occurring in a beaker. Give two er(amples
6. dplain what happens when a zinc rod is dipPed io Cuso4 solulion ?
7. What are halfcells and half c.€ll reactioDs ? ExPlain with examPlcs'
E. Writc the following redox reactioDs usinE halfequations-
(,) zn(r) + pbcr2(44)- Pb(r) + zrclz@q (i 2Fe3+ (aq)+21- (aq)- l2(q+2Fe2+ @4)
ii;4 *t i"t ,"a"runt is reduced ? 'Ib what I (iv) which reaciant is the reduc€r ?
[Ans. (i) ZD(,r) Zt]+ + ?t- (oxidation), Pbz+ (oq) + 2e- Ptt(s) Q"duction\
R
- and Zn is the reducer'
EE
- ZD2+, Pbz+ is reduced to Pb; Pbz+ is the oxidis€r
Zn is oxidised to
2l- 2r- (uidotion)
AR
- -
NaisoxidisedtoNa+andCl2isreduccdtoCl-;NaisthereducerandCl2L\theoxidiser'
IIT
l&
R
Discuss bnefly tho functtoo of the salt bridge iD aD electrochemical cell.
EE
19. Give the conslruction of S.H.E. What is its standard reducrion potcntial ?
How does it help ro
delcrntinc thc standrrd elcclrode potentials ofolher clements ?
AR
ofelements ?
N
Why docs the blue colour oI copper sulphate solution ger discharged when
IA
/Fe =
23, Arra,gc the lorkrwing nretars in increasiDg order of rcactMty. which
one wi be thestrongest reduciDg
agent and which is the wcakest ? Mg, Na, Ag, Cu, Fe, Zo
Ap,p.lT,lCI,N:Al-,,LJ,.,5E-Fuil-,'INiFoKM l,ON
ion Number
(o N.) or
cases the
el(amPle,
F
(a) Oxidation number of Cr in CrO5
x -Z R
or x= + lO(wrong)
method: 6r O", ot '**5x(-2)=0
EE
(i) By convenlional
be nrore than +6 siDce it has 5 electrons in
because the n]a(imum O N ol Cr cannot
AR
is
N
o
IIT
CaEe IL When thc corrwuryl co aiw covabnt ond coqdinde covolenl bondr. Tb calculate tho oddation
number ofatoms in such molecules, the folloring rul€s are generally used.
(a) For eoch covalertbnd between two dbtimils atoms, auign ot uitlotbn ruonbet d +1 to lhe less
elecffonegalive Ltorn qid electonegolive elemenl.
-l to the more
O.N. of the two carboo atoms in CH3COOH may bc calgllated 8s follows :
For cxample,
HO
n-Ll--o-,
#'
q is attached io three H-atoms (less electronegative than carbon) and oDe -COOH
group (more
electroocgative than carboD), therefore, O N of Qis 3 x(+ 1)+x+ 1x(- l)=0 ot x= -z
Ct is, however, attached to one oxygen atom by a double bood, one OH (O.N. = -1) and one CHr (O N'
= + I ) grouP, therefore, O.N. of Ct is + r +r x(-2) + I x (-1)=0 ot x= +2
lf, however, the covalent borld is berween two similar atoms or betwecn two similar atorDswhich are further
attacbed to similar species, eacb atom is given an O.N. ofzero. For sxample, the cEntral Catom in carbon suboxide
(c3Oz) has aD O.N. of zero while each terminal carbon has an oxidation state of +2-
o =tC= 3 =B= o
Similarty in terrarhionare ion R
(SlOt-), O.N. ofeacb of the S-atoms linked with cach otber in the middle is
EE
zero while that ofeach ofthe reamining two S-atoms is +5.
oo
AR
-o-.rJ-3-3-*5J-o-
C
JJ
S
N
IA
(i) If a coordinate bond is formed between sane atoms or dissimilar atoms bul lhe donor alom is less elecio'
negafi)i ion the acceplor atofi, assign on oidotion number of + 2 to the donor atom ond -2 lo lhe otot L
^ccePlor
(ii) Conversety, il the donor atom is more elzcffonegotive tlun the occePlor alot\ neglect he contribution of
the coordinate bond.
The folloering examPles will illustrate the above rules :
oxidation number ol c in H-N 2 C. Herc rhe contribution of coordiDatc bood is neSlected because
the donor atom, I..e' N is more electrorregative than the acceptor atom, |..e., c. Thus' the
o.N. of N in H-N c
since it has three covalent bonds. Thus,
'
remains to be
-3 +l-3+r=0 or x=+2
1x(+l) + 1x(-3) + x =0 or
(for H) (forN) (for C)
Thus, lhe oxidalion number of C in HNC =+ 2,
\
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9154 !,ratlt, , :' Neut Course Chemistrglfifi
ADOITIONAL UgEFUL INFORMATION contd.
Cinse lll. l*hen the compound contains two or more olornt of the wtu elencnt in d.iffereru oidalion slates.
For example
(a) Oxidation Dumhers ofS atoms in NarSrO,
+1 \_2
(i) By conventional method : Na252 03 or 2x(+1)+Zx+3 x(-2)=0 ot x- +Z(wrong\
But this lvrong because both the sulphur atoms caDnot be in the same qidatio! state as is evideot fiom
is
the fact thalwhen NES2o3 is trcated with dil. H2S01 , oDe S atom gets precipihted wbile the other gets coNrrted
into SO2 . The oxidatioo oumbers of these two S atonN can, howevcr, be determined by the chemical boDding
rnel hod.
s
(ii) By chemical bondirgmethod. The strucrure of NES2O3 is Na+ -O - $ - O-nu*
A
Since there is a coordiMte bond between ihe two S atoDs, therefore, the acceptor S atom has an O.N. of
The O-N. of the other S atom can be calculatcd as follows :
-2. 2x(+1) + 3t(-2)
+, + 1x(-2) =0 or +2-i+x-2=0 or ,=+6
(for Na) (for O atoms) (forcoordinatc S)
Thut, the tE/o S otomt in NarSrOrhave oxid.ation number! of and +6.
-2
(r) Oxldation trumber oflron atoEs in magretic oxide (p.3Oa).
R
EE
(i) BJ conyentional method. ierO4nor3x - 2 x 4 = Oorx - + B/3.
AR
(ii) By ttoichiometry. Fe3Oi is knowD to be a mixture of FeO aDd Fe2O3 having the composition j
C
The value of 8/3 for the O.N. of Fe as obtained by conventional method is infact the average ofthe actual
IA
2tut
Average o.N. orClinCaoct2is 6tro, z, , z- 2 = o or x =0
(ii) By stoichiometry. The composition of breaching powder is ca2+1oct-;cr-. Here o.N. of cr in ocr-l
is +l whilethatinCl- is-1 and the average of two oxidation oumb€rs = I x + I + I x _ I = O.
\\
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REDOX REACTIONS 9/ss
A + HrSO. ASO.+H,
Mol. wt.
AClr+C-
C
zBCt+D _ Dc.t2+ ZB
IA
.
No tt ctlotr
Eq. wt. as a reductant is 63/63 = t.
AD& (i) A re€cts with tl2SO1 to libcrate H2 but
Since r.j : Hory does Cu2O act os both oxidaot and reduc-
D does not, thercfore,,4 lics abwe otd D lbs tsnt ? Exphln rvith proP€r rtactions showing
below H it th chccqlunicd *ria the chrrge of oxidation nuEb€rs in each ex'
(ri) Fbrther 6ince D displsc€s B trom BCl, therc- ampfe. BenBalI3.E.2o04) (Wen
fore, E of D is lou/er than that of B, ic., D lies Ans" Cb2O uodergG disproportionation to form
abovc B in thc clectrocbemical serks.
C1.r2+ and Cu.
From (i) and (ii), the order of inqeasbS E" of tbc
four elcmoDts ie., A H, D, B. 2cr+ (oq q4 cuz+ (aq) + cu (s)
(ui) Since C displaces A tom ACl2 but not E Tluu, Cu+ or CurO acts bolh as an oidont a.\ r'ell
hom EC12, therefore, E" of C is louer than that os a rcduclanl
of A and that of E is lo$/er than that of C. (i) Wbeo hcatcd in air, Cu2O is oxidis€d to CUO
From (D, (n) and (iii), it is evidcnt that thc owo, +1 +2
ordcr of increasing elcctode potcttials ol thcse CUO+1/202-2CuO
five elemotr is : E, C, A, H, D B. and Cu2O ocls os o teduclont and reduces o2lo
3. Wbot ls ttre diflcrctrc! iD the defiriilotr of ![
Q.
equivalc[t i[ alr oclil-bosc re{ctlo[ rnd oD d-.
equivalctrt itr an orddstlon-Educdor r.sctloD ? (fi) When heated with CurS, r7 oxidises 52- to
(DJ.I Roldn leeol SO2 qld hence Cu2O acrs ss an oxidan,
A$. EquivaLnl tnigfu in acid-batc Eacti@t is, llre +1 +1 0
weight in grams which suppliG or acc€pts one 2Cu2O + C!2S 6Cu+SO2
mole of H+ ions.
-
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9/s6 Pradeep's
r.! n Bolance the following equations by oxidation Step 1.'Ib determirre unreacted Mohr's salt.
number mcthod ; 50 cm3 of diluted Mohr's salt
(i) S + IINOs... SO2 + NO2 + H2O
= 10 cm3 ofO 1 N K2Cr2O?
(ii) P{ + NaOH + HrO-* PH, + NaH2PO2.
(We* Bensal l.E.E. 200O .. Normality of diluted solutioD = 0 02 N
Ans. (i)S + 4HNO3 +SO2 + 4NO2 + 2H2O Mol. wt. of Mohr's salt = 392
.. Amount of uDreacted Mohr's salt present in
(ii) P1 +3NaOH+3H2O .....* 250 cm3 solution
PH3 + 3 NaH2PO2
O.O2 x 392
i; I'tit ) Bt rll\
|\fiLm L 6.70 g of an alkall metsl oxalat€ was Amount of Mohr's salt used = 10 -I 96=804g
dlssolvcd per litrc ofthe solution. l0 cml ofthb solution From balanced equation,
requlrtd 20 cm3 ol 0'01 M Potasslum pcnnanganate 2 Moles of Mohr's salt (i.r. 2 x 392 8) react with
solutloE iu acidlc medluD What k thc atoBlcweight of one mole of MnO2 = 87 g
the alkali metal .. 8 049 of Mohr's salt will react with MnO2
The balanced chemical cquation for the
redo( rcaction is R7
=2'3g2-x804E=o'8s:8
2 KMnO4 + 5 (COOMb + 8 H2SO4-
Now 0 892gofpure MnO2 are Present in 1 5Iof
IqSOa + 2 M[SO{ + 5 M2SOa + 10COz+8H2O pyrolusite
wbere M is the alkali metal R
EE
.. %age of Mno2 in pyrolusite = TP x 100
Let Ml be the molarity of the alkali metal omlate
AR
Let A be the atomic Eeight of the alkali metal. reduced by metallic zinc. The solution required 34 25
IA
.. Mol. wt. of (CoOMt=2A+S8 cm3 ofO l N \CrrO7 solution for oxidation. Ilowever,
IIT
t'rohitttt J. 12.53 cm3 of 0 051 M SeO2 rescts thrs liberated requlred 12.12 cm3 of 0.1 M NarSrO,
solutiotr for titratlon. Whst is the perccntage ofcopper
exactly with 25.5 cm3 ofO.1 M CrSO. *hich is oxidised
in the ore ?
to Cr2(SOa)3. To what oxidation state ls the selenium Solution. The complete balaoced equation for the
colvert d during the reaction ? redox reacdffi is
Solutior. Let O.N. ofSe in the new compouDd =r 2 Ct2+ + 4l- + 2S2O3-* Cu2I, + SrOfi- + ZI-
duced-
J No- of moles of s2O3- ussg = 11:14 )< 6 1
..- SC+ + Cf+
= 1.212 x lO-3 moles
O*,O,r.OJ Fronl the balancEd equation,
Now 12.53 cm3 of0.05l M SeOz
2 moles of SrOr2- reduce Cu2* = 2 moles
=12.53x0051 . . 1 .212 x 1O-3 moles of S2O3- will reduce
= 0.64 millirDoles of SeO2 R
EE
Cttz+ = 1.2t2 x l0-3 moles
and 25.5 cm3 of 0.1 M CrSOo = 25 .5 v 6 .1
AR
11,"
..
IIT
Sn = (Roo @.1993') = 2f
S
..
IA
Wt. of IqCr2Oz preseDl in 10 cm3 Step 2. Tb find out rhe amouttt ol Ny'tCOr
IIT
,.<
_ffix10s Multiplying nrst Eq. Siven in tbe questioD with 5
and secoDd Eq. with 4 to caDcEl Fe2+ aDd then
Mol. wt. of lqCr2OT = 294 on adding, wc 8et,
- 3 x 0.0001? = 0 00051 mole iodin.. Calculate the percentage ofMnO2 ill the
srrDple (At wt of Mn = 5t. (Rn*ee 199O
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BEDOX REACTIONS 9/59
Ans. Step l.'Io write the complete equalion for the 2 Na2S2O3 + 12 -- NES1O6 + 2 NaI
redox reoalioru
SuppG€ sreight of IqCr2OT in the mixture = rg
MnO2 + 4 HCI -.MnClr+Cl2+2H2O
Then weight of KMnOI in tbe lllixture
zKl+Clz 12KCI +\
= (0.s _r)t
Iz + 2 Na2SzO3 NES.O6 + 2Nal
- Iodine producrd from x S Y.2Cr2O, = xxg
ffi
Mnoz + 4HCl + 2KI + 2 Na2S2O3 ...- Iodine produccd fmm (0.s - r)t XMno.
MoCl2 + 2KCl + N%SaO6 + 2NaI + 2 H2O
-ff'10's-'1r
Stcp 2. Tb calculate lh. prcentogc of MnO 2in the Tbtsl iodinc produced
sanple x -r\ -
No. of moles of Na2S2O3 prescDt in 30 crn3 of 0 . I 291Ll27O(0.5
-762 316
=
"
IA
Q 5. 0.5 g mlxturc of KrCrrO, and KMDOa wos endtc lroo ls clnycrtcd lnto Fe'+ alotrgwitb
IIT
=
N
2 N%S2o3 + 2 KI + 03 + H2SOa
= 5 x 0.0064 - 0.032 mole FeSO4
IA
- + 2NaI
oz + Iqsoa + H2o + NEs1o6
IIT
t
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REDOX REACTIONS 9/61
., % of 03 by rveight
10 I- .--.---.+ 5 12 + 10 r-
-ffi*rc0 =e .stt*
2IO; + 12H+ + l0I-......- 6 12 + 6IizO
No. of moleculer in 2 x 10-3 mole of O,
2 S2O3- + Iz SlO2- + 2l-l x6
-2 x 10-l x6.U22xlP -
=12044x1021 2lo; + nH+ + 12 S2o3- .._
., No. ofphotoos required = I .20{4 x l02l
6SaO?-+2I-+6H2O
Q.E An aqueous solution of 0.10 g KIO3 (formula
wGlgtt = 214.0) was trcat d witb an excess of No. of moles of KIO, =
KI solutlon. Thc 6olutlo! sos acldlllcd with f;]
HCl, The liberat d I, consumd 4S.0 ml of No. of moles of Na2S2O3 ,"6g1s6 = x e,
thlGulphrtc soludotr to dccolourise the blue 2lq+
which are present in 45 0 ml.
sarrch lodltre complcE Colculatc tie Eolsilty of
sodlum thlosulphste soludor. (IJ.T l99E) Hence molariry of Na2S2O3 sol.
Ans. The readions involved are : 0.1 6 1000
x
= --r-i1- x -73-
2IO; + 12H+ +10c-+6H2O+12
= 0.0623 M.
R
EE
AR
G)
(4) +1 (r) 0
S
(c) -1 (d) + 2.
N
IA
-
the correct coefficienls of the reactaots for the
(b) 02 + 2H2 - 2HzO
balanc€d reaction are : (c) Na + H2O - NaOH + 1 ,/ 2H2
Mnoa- qo?- H+ (d) MrC\ - MnCl2+ | / 2 C\
-<6) 2 s 16 (A-I.LM.S. 1993)
-cu(No3h+No+No2+
The co€fncients of.r and I are 16. The oddatioD Poteotials of A and B arc +2 37 V
(o)2aDd3 g[7 afi 6 and + t 66 V respcctively. In a chemical reaction,
(c) I and 3 (d) 3 afld 8. (o) Awill be rcPlac.ed bY B
("fi s ): lt\I l: lt)')tl - (r) Awlll replace B
10. ln which of the following Pairs, there is Sreatest (c) A will not replac€ B
differenc€ in ihe oxidation number of the under- (d) A and B will oot replac€ each other.
lined elements ? tt).t!\ tl..l.'l: 1996: l'h (.1 'l: 19971
(a) NO, and NzOa (6) f2O5 and & Olo 17. Which among the follo$'ing is the strongest reduc'
(c) N2o aDd No -/tqo2 and SO3' ing agent ?
ll).(.1; 1991)
R
Given, Fe2+ + 2e- + Fe (-0'44V) '
EE
11. In the reac on, Ni2+ + 2 e- .+ Ni (_ 0.25 V);
+ H2S ...- 2FeClr+2HCl+S
AR
2FeCl3 * 2 r- ......-
tnz So (- 0.14 9 and
qidizing
C
(a) lDYTez+
IJ.l1.U, l99li)
IA
(d) II2S acrs as rn crddizing agent' lE. Y'lithout losinS its concentration, ZnCl2 solution
tU P S l;A I:19t)('| cannot be kePt in mntact with
(c) Bromine is neilher reduced nor oxidised s8 , S2F2 , Hzs resPeativelY, are
lt.,
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REDOX REACTIONS
9/63
21. A gas at I
8tm is bubblcd through a solution 2t, In the givcD re3dion,
containing a mixture of 1 M Y- aDd I M Z- at
&Cr2O7 + XH2SOa + YSO2
25oc. If the rcduction por€ntial of Z > y > X, -
ihen IqSO4+Cr2(SOr3+ZH2O
(a) Y will Gidize X and not Z X"Y,Zarc
(6) Y will Gidbc Z ard Dor X (a) l, 3, 1 (b) 4, t,4
(c) Y will cnidize both X aDd Z (c)3,2,3 (d) 2, t,2.
(d) Ywillreduce both Xand Z (t.t7: tsse) lR.H.U. 1991.20t)01
2L A ion M3+ lces 3 clcdrons, its qidatio[
mf,aal 29. The oddation DumbcrofiroD is Fe3O{ is
number will b€
(o)+2 (D)+3
(a) +3 (D)+6 (c) 8B (d)28.
(.) o (d)'-3 tc'.tt,tt.t tccct (C.B.S.E. l!n[.T 1999 ; HoD,ana C.E.D.T.2000)
23. 'Ib an acid solution of an anion, a fcw drops of
3lL Which will bc ihc proper altcrnative in pl8cc of A
KMnO4 solution are added. Whih of the foitcm,-
in thc fo[oying cqua[on.
iDg, if prescnt, will not decolourisc the KMnO4
solution ?
2#+ 1aq1 + saz+ 1aq1+ 2Fe2+ @qt + A
(a) Sna+ (D) Sn3 +
(d) co3- (6) NO2-
(c) Sn2+ (d) sn.
(") s2- (d)Cl-. tD L:.t:. teee) (1t.PC.8.8.2000)
The pa ial ionic equaiion, 31. Numbcr of mol6 of Iqq2O, rcdued B , mol€
C.x2O4- + 14 H+ a6s--2G3+ +71\O ofsnz+ is
suggests that rhe equivalent urcight of Cr2O?- will R
(a) 116 (b) 18
EE
be equal to it! formula sreight divided by G)a3 (d) 1.
AR
(:.t:,.2o0ot
(a)+7 (b)+6
IIT
ANgWE
2-l.g ??.b 23. a 24. b 2s. d
31. b 32. c 33. c 34. c 35. c
26. b 27, a
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9/64
3E. In the standardiztioo of NES2o3 usin BY\ct2ol (c) MnOa- can be used in aqueous H2SO4
by iodometry, the equivalent weiSht of IqCr2OT is
(d) CrzO?- can be used in aqueous H2SO4
(a) (moleculsr weiSht)z
t I.l 1: :ltt) ) \
40. Standard electrode potentials are (D) CaqO4 + 2HCl CaClz + HzCzO+
IIT
FeE = -0,14v,Fe+3zFe+zEo-o71y
-
Fe2+ .t (c) Mg(OH)z + 2NHoCl- MgCl, + 2NH4OH
Fe+2, Fe+3 and Fe blocks are kept together, ihen (d) Zn + 2AgCN 2Ag + Zn(CN)2
(a) Fe+3 increases
- (A'lEElt'2t)02)
(D) Fe+3 decreases A smuSSler could not carry gold by depositing iron
oll the gold surfac€ sinc€
(c; Fe+2 z Fe+3 remains unchanged
(o) Gold is dens€r
(d) Fe+2 decreases (b) Iro[ rusts
(c.B.s l. P.'tlr200I) (c) Gold has hiSher electrode Potential than iron
41, The reductioD Potentials of Zn, Cu' Fe and Ag are
(d) Gold has lovrcr electrode potential than iron
in the order :
(Kanutk*a C'Ii '1: 20t2 )
1,jrrno,, necr, R
EE
flp, ="r:,i=^;,'"==2T:r,,==t;,rr==rul,,"==1
-(r) MnO;, CrO2Cl2 (e)o=l,b =6,c =4and.t=6,y=Z,z=3
AR
(c)lFe(cN)613-,[co(cN)]l
C
(d) [NiCl4F- tcocll]- whereas silver does not. The E.M.Ii of rhe cell
\t.t 2001)
N
, 7:
g).
IA
:1-y-
IIT
-0 41, + I 57, + o.7'.- and + I ,97 V resDectivelv. -ftCurrent flows from zinc eleclrode to coDDer
For which one ofthesc metals, the change in oxid;- electrode
tion state front + 2 to + 3 is easiesr ? {€}&tions move towards copper electrode
(a) ft (D) Mn (d) Carions molr'e ro$rrds zinc elecrrode
A^JSWERi
it.I il:i 4E. c 4e. b 50. c sr. tt s2. b 53. o s4. b ss. d
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9/66
1r 's Nc.t Coursc ChemistrAWII)
L'
t'
M8(NO3h is beiDg electrolysed using inert (c) sol- (d)*- rc.nv.r zoo,tt
electrodes. The values ofstandard electrode Poten-
tial (reduction are Ag+'/Ag + 0 80
Potential) -
HINTg/EXPLANATION9 to
1. Sodium amalgam is a homogenous Dixture ofNa
o.N. of two N aloors in Y inqcases by 10,'e thc
tolal O.N. of two N atoms in
and HE and a\ such Na exists in thc elementalstate
aod hence ils O,N. is zero
R Y=-4+10=+6.
EE
+1 ..
O.N.of eaohNis\ = + 6[2 = +3.
2. MnO4-*5"--Mnz'
AR
resPectively are :
3Cu+8HNO3
N
.'. 1 mole of Mr+ will lote el€ctrons = 5/1 67 -...- t 2NOz + 2 IIzo
IIT
Cu + 4 HNO, Qu(NO3)2
= 3 molfs (awox) ...(,,)
Since Mr+ changes to Mof (where o N' of M = Adding Eqns. (t) aDd (ii), we havc
+ 5) by sccePing 3 clectrons 4Cu + 12HNO3
.. oxid8 on stste of M,l"e,, 4 cu(No3)2 +- 2No2 + 2 No t 6 I{2o
x=+5-3=*2
or 2Cu +6tlNO3 -......-
4. The balanced redox equatiotr h
g+ 2 Cu (NO3)2 + NOz + NO i 3 I{2O
2 MnO.- + 5 CrOl- * 16
ccflicientsr and/ of Cu and HN03 resPec-
2Mf2+ +- loco2+8H2o
Thus
tiwty are 2 aod 6.
-+6+2(_3)=0.
N
reduce Crro]-.
Lg
2' Use the lolloring
Thequesools
key to choGe the sPPrcPrhte oNwer'
Utf assertiou and reason ore CORRECT aDd reoson ls thc CORRECT cxphnotlon ofthe
acsertion'
laif exPlslstlon ofthe assertlon'
iolttoo,t rnd reasol are CORRECT but reasor ls not the CORRECT
"""."Oor
(c) IfossertioD is CORRECT but thc resson ls TNCORREC'I'
(d) Ifboth ssscrtioD and reason ore INCoRRECT'
Assertior (Columr l) Reoson (Column 2)
1. Blue colour of CuSO4 solution fades away whcn Cuz+ ion is oxidised by Fe
iroD plate is Plac€d in it.
Copper liberates hydrogen from a dilute solution HydroSen is below copper iD the electrochemical s€ries'
of bydrochloric acid.
u.I.I.M.S' l99s)
Zinc displaces copper from copPer sulphate solu- E of Znis-0 76 V aDd that of Cu is + 0 34V
(A.I.I-M.S. 1999)
tion.
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BEDOX REACTIONS
9/69
R
4. The oxidation number of N iD NI3 is
EE conductivity, has copper in midation state
5. The teDdency of an electrode to gain or ......-.......... Assume that the rare eartb element yt.
lose
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1ee4)
S
O
IA
y
IIT
R
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AR
C
S
N
IA
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QJ N! OfT
)i
I
i Concentration ol orcs,
Concenttation ores, reductiory' oxidation (eleclronation/
(eleclronation/de- electro- nalion), refining ot metals. i
t*.. -. _ - _.*.* **
,"--,""., ".'",,,.-.,'*,*,"'"..,..;
variety of nuclear
Elemerts are the basic units of all types of
matter in this universe. How were these ellments
eutroos emitted b
originally formed and how are they distributed on R + lue .....- fiwg + Ut
EE
ffNe
earth ? What are their modes of occurrence in the
llt'to + ln ..-.* lrMo + /-ra)6
AR
earth's crust and how are they obtained iu the pure +neutrino
hrm ? These are some of the interestiog qu..iion.
C
,l
which come upin our minds and in this uiii we shall
W+
S
-?p
N
utlt
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1o12
Volatile elements : C, halogens, Hg, Pb' Zn (i) Based upon the stsbilities of tha nuclei,
elements with even atomic numben are more abwt
Non-volatile elemenls ; Fe, Co' Ni, Si, Be, Ca
dont than those wilh odd atomic numbers.
It is, therefore, reasonable to believe that ter-
(ii) Thehig! abundance ol iron h due to its ltigh
restial distribution of non-volatile or less volatile
nuc\ear binding energt
elemenG would be somewhat similar to the overall
cosmic (i.e. in the universe) distribution. On the (iii) The low ligl er elements
abundsnces oI
other haad, volatile elements are greatlyless abun- ruch as Li aft
Be and B due lo thei ability to rcact
dant on eatth due to their loss during the high wih more 4- Particles Ioming other elements' For
temperature periods accompanying the formation qMPlq
of the earth.
lne + lue ""'.' l'zc
Cosmic abutrdances of elements.t The cos-
mic abundances of elements are shown in Fig 10'1' 103.1. Condensatlon Processes
These data are only approximate because of the The non-volatile elements becauso of their
following reasons : higb melting points underweot condensation
without any loss at relatively high temperatures
and thus appeared as minerals in high abundances.
The moderitely volatile elements such as Ag, Zn,
1',. Ge, Sn and F, however, condensed in lower abun'
$a
z
dances while volatile elements such as Cd, Hg, Pb
and halogens (other than F) condensed in rather
o-
zo relatively low abundances. Thus, the early conden-
R
sates inilude metallic iron (with 12'5% Ni) and
EE
dl
u4 diopsidz (Ca Mg Si, 05) aad anofihite
AR
t-
5^ (Ca Al, Si, Or).
C
I
l-a accotnl for 3-4Vo of the earth.
.U
1032. Zonal DlsHbutlotr
ATOMIC NUMBER ---+ The earth mainly consists of the following hvc
zones :
-
1. The atmosPhere
2. The hydrosPhere
The three inner zones, i.e.,lithosphere, mantle Xe (< l%). The atmosphere extends not more
and core are studied by seismography. These are than 60 km above the surface of the earth.
distinguished on the basis of properties which 2. The hydrosphere. The liquid phase oI the
depend upon density and elasticity. edrth (oceans,lokes etc.) is called the lrydrosplure.lt
Let us now briefly dlscuss the comPosition ol covers about 807a of the earth's surface. There are
these zones. a large number of elements present in sea water.
1. The atmosphere. The gascous mixture sur' 3. Th€ crust or the lithosphere. The upper
rcunding lhe earth is called the atmosPhere. It col- solid phase of the earth is called the crust or the
tains mainly nitrogen (78'W%), orygen Q0'957o) lithosphere. Its thickness various from 10-50 km
and other gases such as COr, He, Ne, Ar, Kr and (Fig. 10.2). It consists of three tlpes of rock.
R
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C
S
(l) Igneous rocks. It is believed that the (ii) Scdimentary or Strattlied rocks. The
temperature deep down the earth is very high. The weathering (selective extraction) of igneous rocks
ertre,nely hol mateial present inside the eulh is by water, carbon dioxide and humic acid (organic
called magma.D\e to earthquakes, some Yents are acid formed when water passes slowly through a
created in the upper layer of the earth. The high mass of decaying vegetation) dissolves
temperature inside the earth sometimes forces the Na+,Mgl+, caz+,Fe2+ etc. leaving behind in-
magma out of the earth',. surface through these soluble residues consisting of TiOr, Fe2O3 and
vents in form of volcanic eruptions. ThLs magma SiOr. These insoluble residues are ultimately
gets spread ovcr the surface of the earth. With
broken into fine pieces called sediments. These
gradual cooling, over the years, it gets solidilied in
sediments are then carried awaay by water to river
the form of rocks. Thtts, igneous rockt are formed by
banks and sea beds where they get deposited. With
gradual cooling and solidification (i.e. Iructional
the passage of time new layers are deposited over
crystallization) over billions of yean of the molten the old ones. The bottom layers are ultimately con-
moteiql coming out oI the eatTh's surface duing verted into rocks by the pressure of overlying layers
volcanic eruplions. The word igneous implies
and presence ofcementing material like lime. Thus,
formed by fire. These are mainly made up of sedimentary rocks are composed mainly of
aluminosilicates along with certain other ions such
minerals such as dolomite, limestone, silica, iron
as Fe2+, Mg2+, ca2+, Na+ and K+. These rocks
oxide, clay etc. The sedimentary rocks are also
cover about 4/5th of the earth's crust. Some impor-
called stratified roc&s since they occur in form of
tant examples of igneous rocks are : grazite, basalt, layers. Limestone, sandstone, dolomite, shale etc.
gabbru, etc.
are some important examples of sedimentary rocks.
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1014 Ne.a,
Sidcrophil Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag,
Re, Os, lr, Pt, Au
5. The core, On the basis of type of phase, the Silicates aDd oddes of metals like
core has been divided into two parts, viz, the outer
Be, Al, Si, Y, l-a, Ac,'fi, Zt, Hf , T-tr,
core and the inner core. Whereas the inner core is
Y Nb,'Ih, Cr, Mo, \Y U
a solid of about 650 km depth, the outer core is a
liquid of 2100 km depth. Both these ParG maidy Atnrophil F, Cl, Br, I, B, C, Si, N, O, He, Ne, Ar,
consist ofFe-Ni alloy.Apart from Fe and N| other IK, XE
elements alloyed with iron in the core are Co, Pd
and Rh. Seismic studies also suggest the presence R
From the above table, it is evident that an
EE
of some orygen or more probably sulphur in the element may be prominent in more than one
geochemical category. For example, orygen can
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core.
Goldschmtdt Classificatlon' According to be regarded both as a lithophile and as an at-
C
eorth is called the iron core or the metallic core or Earth's crust is made up of light clements
siderophil (sideros it Greek means iron). This such as orygen, silicon and aluminium. Oceanic
covers both inncr and outer cores as meutioned crust is mainly basalt (which also contains mag-
above. The elements present in siderophil are nesium and iron). Continental crust is mainly made
called iderophiles. up of t*o types ofigreous rocks :
2. Chalcophtl. Thz loyer ol the eotlh sutround' (i) Light tockr, i.e., granite and related types
ing lhe iron corc (i.e. mantle as mentioned above) li containing 707o SiO2 together with AlrOr.
called chalcophil. Since this layer mainly contains
sulphides of Cu, Zn, As and Pb, therefore, tbe (ii) Heavy roclg i.e., basalt containing40'50Vo
elements present in this layer are called chal' silica togetber with MgO.
cophiles (/<iral&os in Greek means copper and Aluminium is the second most abundant elc-
brass). ment in the light rocks andmagnesium is the second
S.Lithophil,The outermost po,Tion of the earth most abundant element in the heavy rocks.
is caltedlithophll (,lit&os in Greek means stone) and 112 elements are knowlr at Present time. Out
the €lements present iD this layer are called of these, 88 have been found in nature and the
lithophiles. remaining have been synthesized. Orygen con'
4. Atmopbll. The gaseous mirture sunounding stitutes nearly half (a9'5) and silicon one'quarter
E crust or the lithosPhere is called the atmophll. of the total mass of elements in the earth's crust.
The sixteen most abundant elements in the earth's
The distribution of the elements in these four
crust and their percentages by weight are listed in
different zones is different as shown in'Ihble 10.1.
Table 10.2.
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PRINCIPLES AND PBOCESSES OF EXTMCTION OF ELEMENTS 10/s
T\vo poins which emerge from the about table '10.6. Oceans as a Source ol Elements r"rftirg*;,++irr',i
are :
Oceans are a rich source of many useful
(i) Elemens with low atomic numbers con- substances, nutrients and minerak;. For example,
stitute a major porion of the earth's crust.
(i) Oll and natural gas octur in continental
(li) Elements with evco atomic numbers are shelf sedimentes.
generally more abuldant than elements with odd
R
(ri) Gold and manganese are present as sedi-
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atomic numbers, There are, hoq/ever some exc€p-
ments on the ocean floor.
tions. For example gases (with even atomic num-
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f:ir,i+.:rjii li.iii.ii:i.,ii:,,i,:
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Many elements are accumulated in living or- (i) Igneous rocks consist ofaluminosilicates of
ganisms. For example, sodium, pota-ssium, calcium etc. Rain water con-
(r) Iodlne rs sea weeds, (li) vanadium in sea taining dissolved CO, dissolves these elements as
cucumbers (ilr) Magnesium in chlorophyll, the thei.r bicafionates wlich go ioto sea water leaving
green colouring pigment of planLs. (iv) Potassium behind clay and sa nd (called detrias cloy) .
and iron also present in plant life. (v) Carbon and Igneous rock
hydrogen are major comtituents of all organic
CaAtStos
molecules (Dimoleczles) present in our body in one
Co I c itgn o lumin dtili c atc
form or the other. Besides, these living organisms
contain different elements in different parts. For + KAIS3O8 * Rain water
example, (i) lron in haemoglobin (blood). (PoL olumhatilica,c) (H2o + co,
(i) Zlnc in eyes of some animals and the + NaAlSi3Ot
enz,,rne carbonic anhydrase present in cells. (Sod" oluminNidcotc)
(iii) Tiaces of Mn, Fe, C\ ln abe chloroplqsts. Stream ofwater + Detritus clay
It may be noted that very little is ktrown as to (ca2+, K+, Na+, HCot) (claY + Sio)
why a particular elernent is present in a specific (ri) Marine organisms convert Ca2+ and
region of the living organisn. However, it is known HCOI ions to form CaCO, (shells) which form
that their deficiency causes many disorders in the sediments,
body. For example, deficiency of iron causes
anaemia while lhat of iodine causes goirre. _ _ Irarinc organisms
(rrr) HCI injected by undersea volcanoes the air occur in the native state. For example, gold,
reacts with HCO; to form chlorides of Na, K and platinum, noble gases etc.
(ii ich are
Ca in sea water
HCI+HCO| CI-+H2O+CO2 readily carbon
dioxide state in
-
The relative abundance of elements in sea form of their compounds called minerals.In the
water is shown in Fig' 10.3. combined state non-metals are found in the
reduced form while metals are found in the
oxidised form such as elements are generally
10 present as oxideg carbonates, sulphides, silicates
etc. as shown in Thble 10'3.
1-.Ult lt !U.-l' llrrpot'tant'l\pes ot ()l'es
Ore type ExamPles
I
o) Natlve
Y
J
O ta-2
Oxides
O
zo
o
104 R
EE
Carbonates
AR
CI NaMgS CA K C BT B ST Si N Li AI Rb
C
'Non-evaluative
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PRINCIPLES AND PROCESSES OF EXTRACTION OF ELEMENTS lOlt
(i) ffssa and Blhar have the largest deposits occur in the combiled state.In the contbined state,
of ores otiron, manganese, chromium in addition to metals usually occw in the oxidised form, (e.9.,
coal, mica and phosphates. FerO, AlrO j, SnO, MnOr) while non-metals
(ri) Madhn Pradesh and Maharashtra have occur in lhe reduced fotm such as X- (X = Cl, Br,
sizeable reserves oI maganese, chromium and I). Silce the modes of occurrence of metals and
bauxite. non-metals are different, therefore, their methods
(ra) R4lasthan is rich is non-ferrous metals of extraction or isolation from their natural sources
arc differett. Metals orc usudlly oblained from their
like copper; zinc atd lead
oidised forms by reduction while non-melals are
(rv) Thmll Nadu has large deposits of iro4 obtained from lhet reduced lotms by oidqtion.
manganese, mkq limestone a\d lignite. Whereas reduction is btought about by eleclton,a-
A number of industries are producing iron, tiot, i.e. ; addition of electons dinctly ot indirectly,
aluminium, zinc, gold etc. The Steel Authority of oidation is canied ou, b) dc-clcctronation, i.e., by
India (SAIL) is producing over 10 million tones of removal oI ekctrons dircctly ot indirectly.
steel through a number of steel plants. 10.10.1. Extractlon of Non-metalllc elements
1o i)- Occurrence o, Metals-Minerals and Ores,,r,r Non-metals occur in the combined state in the
reduced form. Therefore, they are generally ex-
Majority of the metals occur in the crust of tracted or isolated by oxidation of their com-
the earth in the combined state in form of com- pounds. Consider, for example, the oxidation of
pounds called mluerals. Thus, chloride ion in water.
The nafitral materidls or the chemical com- 2 ct- (aq) + zHrO (t) --.---+
pounds in which the melals occur in the eqrth are zoH- (aq) + H, G) + Ct G)
called minerals. R
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In other words, metals are extracted from Since this oxidation cannot be carried out by
ordinary chemical methods. Therefore, it is ac-
AR
llu mincraltmm *hich the melal ts conventg l! Similarly, fluorine is extracted by electrolysis of
S
*acal is slltil
N
arul econonicel$ an one. Ihzs, their fluorides. Elements like oxygen, nitrogen and
IA
aU org5 are mlnsok ba all mtnemb on t* ors. noble gases are directly obtained from this. In con-
IIT
Eveo l6{D yes6 ago, Indians had a high level ofskill io metallurry. This is evidenl &om the Delhl IroD plllar
Near Kutab Mioar. It is ess€ntially made up of wrough iron (99 .72Eo), carbon (0.08%), silicoo (O.M6%),
sulphur (0.006%), phGphorus (0 1l4%)and margaoese nil. Since40OdD., it has been existio8 without any
rust or siSDs of decay.
Thi! s pdmarily due to the reason that during linishiDg treatment git€n to the pillar, a ihin Alm of magnetic
oxide (FcaO, $as applied on its surfacc.
called crushlng. These small pieces are then out in specially desigrcd tables called Wilfi ey tab les.
reduced to a fine powder with the help ofball mill'
S
N
'A strmp mlll ir r hcsiystrmp or boltwhich riJas and falls on a die bclof,onwlrich c 6hcd orc is fcd from onc sidc. A t nll
mlll, on thc othcr hand, consists ofa bigstccl tank containing a fe* stecl balls ora fcw picccr ofhard stonc likc flint in it. Thc steel
tank is fed with crushcd orc and w'etcr, and rciatcd. Stc€l balls fal! on thc crushcd orc and rcducc it to powdcr.
, F
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10/9
PRINCIPLES AND PROCESSES OF E)fiBACTION OF ELEI\'IENTS
magnetic roller contains the non-magnetic im- The suspension is violently agitatcd by the
purities (Fig. 10.4). In case of tinstone. thc rotating paddiewhich draws in air causing frothing'
iunqstates biing magnetic fall in a heap under thc During this process, the ore particles which
mafoe tic roller while the ore particles i.e. SnO, fall are preferentially wetted by the oil become lighter
in a separate heap away from the magnetic roller. and thus rise to the surface abng with the froth
while the ganguc particles which are preferentially
wetted by water become heavier and thu-s settle
ELEcTfi oI\,lAGNErlc poFJ,,lBEeLJeo down at the bottom of the tank. The froth is
ORE skimmed off. It is allowed to collapse and finally
dried to get the concentrated ore.
If the mineral to be concentrated consists of
NON.
MAGNETIC
PARTICLES
MAGNETIC
PARTICLES
,i..ic
sodium cTanide is used as a dePressant to separate
lead sulphide (PbS) ore from zinc sulphide (ZnS)
FTGUBE 1O.4. Electornagnedc separatisr. ore. This is due to the reason that NaCN forms a
zinc complor, Nq [Zn(CN).1 on the surfacr ofZnS
4. Ftoth tlotatlon. This method is widely used R
thereby preventing it from the formation of froth.
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for the conc€ntration of sulphide ores such as zinc Under tlese conditions only PbS forms froth and
blende (ZnS), copper pyrites (CuFeS), galena
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in lreoting
N
ROTATING PADOLE
ORE FROTH
.:a:::::::::::::::::::::
::::::::::::::::::::::::
:;:;:r1g:-:-!::::::
:_:_:1{.[$:;:_:_:
:::::::1..I:::::=+::
.- ""J#:',sllo'
PADOLE ORAWS IN AIR
AND STIRS THE SUSPENSION
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10/ 10 Pradeep's
of NaOH when alumina (Al2O) dissolves forming (ii) For gold, 4Au + 8KCN + C)2 + 2H2O
sodium meta-aluminate leaving behind impurities aK [Au(CN)rl + 4KOH
which are Iiltered off. Pot. dicranoauratc (l)
AlrO, . 2 H2O (s) + 2 NaOH (aq) + I{.O (f """'r (Solubk compla)
(a) Calclnation.
nrctqls like silver and gold by convetting these metak
S
N
| (Sulphur dionde)
8SOz
(a) Chemical reduction
N
| (Phosphorus pentoride)
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I}pes oflluxes. Depending upon the nature of (ii) Zone ofheatabsorption.ThLs is lower part
the impurities present in the ore, fluxes are clas- of the furnace and the temperature here is between
sified into the following two tyPes : 74.23-1673 K. As the CO, formed near tuyeres
(i) Acidic lluxes' For basic impuities like lime moves up, it meets the descending charge. The coke
or metallic oides (FeQ MnO etc.) yesent in the ore' present h the charge reduces CO2 to CO.
acidic lluxes &,te sr?lc a (SiO) and boru (NarBoOr.
co2 + c--.+ 2co ;AH = + 163 2kJ
l0HrO) ac. are used
Since this reaction is endotherrnic, therefore,
Cao SiO2 CaSiO,
the temperature gradually falls to 1423 K.
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PHINCIPLES AND PROCESSES OF EXTRACTION OF ELEMENTS 10/13
Furmce Double
charg! cuP
(ore + coke) and cone
+ limestone arran9ement
//
Mollen pig iron
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FIGURE 1O.7, Blast lumace for the manulacturc of pig or c.rst iron.
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C
rln K
1123 K. In this region, Iimestone decom- FeO + CO --.---..r Fe * CO,
IIT
(ii) Reductlon or electronation by hydrogen. separated from the other products ofthe reaction.
Hydrogenis alsoused for reducingoxides of metals A few examples are :
but this is more expe.sive than using carbon. Fur- 2Al + Cr2O3 N2O3+ zct
ther, because of its inllammable nature, it is used
only in those cases where carbon does not work. 8Al + 3MqOl - 4AlO, + 9Mn
The oxide of the ore is placed in a tray and heated
in a current ofhydrogen. For example, -r be reduced to metaUic
Likewisc Fero, can
Ilcat iron.
WO3 + 3Hz ........+ + 3H2O w
'fungsten Tungstcn 2Al * FcrO, '---------' Alzo,r + zFe
trioxide
Hcat The molten iroa produced as a result of ther-
Nio + H2 Ni + HrO mite process can be used to weld broken parts of
Ilcat heavy machinery of all kinds, such as girders, rails
MozO3 + 3Hz--------- 2Mo +3H2O etc, This pmcess is calred tbcrmltt weldin8.
olltide nu Molytrdenum
M Dr (lv) Other metals as rcduclng agents. Like
trioxide
aluminium, other electropositive metals can be also
(iii) Aluminlum as a r€ducing agent. Many be used as usually agents. For example,
oxides like CrrOr, Mn3C)a , Fe2O3 etc. are not easi-
ly or satisfactorily reduced by carbon or carbon BrOr+3Mg-'3MgO+28
monoxide. These oxides are, however, easily TiO2 + 2Mg- Ti + 2M8O
reduced by aluminium.
Thc process oJ TiO, + 4Na-r Ti + 2 NabO
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metal vilh llg ,
Instead ofusirg oxides of metals, their halides
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In this process, a nt
N
TiCln 2MSCI2
called thermi'E is ignited in a closed crucible by
IIT
inserting a burning magnesium ribbon into the ig- O) Auto-rtrluc'llon or Self reducdon or Self
nition mixture consisting of magnesium powder electronsdon,
and barium peroxide (Fig. 10.8). This process is
Somc metal sulphidcs can be used for the
called thermite process or the slumlnothermlc
reduction of their own oxides. Thus, when the sul-
process. Metals like maaganese and chromium are
phide oras of the less active metals (whose oxides
obtained by this process.
are unstable towards heat like Hg, Cu, Pb etc.) are
roasted in an excess of air, a part of these sulphide.s
are oxidiscd to their oxides which further react with
more of the sulphide ore to yield the metal. 77ir
Mo POWDER
+ Bao2 process is c4rJed sclf-rcductlon or a[to.rcductlou.
For example,
AI POWDEH (l) ues (s) + o, G) -'-"'r
+ Cr2O3
Hg(8) + So2 G)
or 2 HgS (s)+3 Oz(0
2 -Hgo (s) + 2 So2 G)
FTGURE 1o.8. Alunrinothermic process. 2 Hgo (s) "'-' Hg G) + oz G)
The ignition powder burns to produce a large also 2 HgO (s) + HgS (r)
amount ofheat. As aresult, the metals are obtained
in the molten state and hence can be easily
-)
3 Hg (8) + So2 G)
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PFIINCIPLES AND PROCESSES OF EXTRACTION OF ELEMENTS 1O/15
(ii) zPbs + 3o2 ...........+ 2PbO + 2SO2 (NaCl solution) using mercury cathodes, the Na+
Galcna is discharged atcathode and forms an amalgam. On
2PbO + PbS 3Pb + SO2 the basis of electrochemical series, the liberation of
H, should have occurred at the cathode. However,
-,
Sometimes the sulphide ore may be oxidised
to sulphate which is thetr reduced to the free metal due to high H, overvoltage at the Hg cathode,
by the excess of the sulphide ore. liberation of Na occurs in preference to H, gas.
PbS+2O2....._PbSOa NaCl -----------r Na+ + Cl- (Ionization)
PbSOI + + 2SOz
PbS -----......r 2Pb (Mohat)
(m) 2CurS + 3o', - --+ lQtrzo + 2SO2 At cathode: Na+ + e- ----.-r Na (deposited)
Copper At anode: Cl- - e- , Cl
pyrites Cl+ Cl ......._ Cl, t
ZCt}rO + Cu2S 6Cu + SO2 (il) Electrolysis of alumlna. Metals other than
The roasting of the--sulphides are discussed s-block elements can also be extracted by
above is usually carried out in a reverberatory elecirolysis of fused compounds. For example, in
furance (Fig. 10.6). Hall and Heroult process, alurrinium is obtained
(c) Displscement method, by electrolysis of a fused mixture of purified
alumina (AlrOr) and cryolite (Na3AlF5) at 1150-
Some metals are reduced by displacement by
1173 K, when molten aluminium collects at the
a more reactive metalfrom their soluble complexes.
cathode.
For example, silver and gold are obtained from
their complex cyanides (obtained during leaching) IV Re{ining or Puriflcation of Metals.
by addition of more electropositive zinc metal. RThe metals obtained by any of the methods
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Na[Ag(CN)r]+Zn- discussed above are still impure and hence are
2 Naz [zn(CH) al+z Ag L called crude metals. The impurities generally
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Active metals such as alkali netals, alkaline reduction of their respective oxides originatly
N
reduction of their respective oxides with carbon. (ii) Non-metah -like silicon and phosphorus
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This is due to the reason that the oxides of these formed by reduction in the furnace.
metals are very stable and thus have to be heated (irl) Unreacted oxides and sulphides of the
very strongly with carbon in order to reduce them metals, and
to the metallicstate. Further, at such high tempera- (iv) Substances taken up in the furnacr, e.g.,
tures, metals liberated combine with carbon form- residual slag, flux etc.
ing their respective carbides. Thus, such metals are
extractcd by the electrolysis oftheir molten or fused The crude motals are, therefore, purified or
refined. The method actually used for purification
oxides, hydroxides or chlorides. The metal is
liberated at the cathode. depends upon the nafure of thc metal and the
nature of the impurities to be removed.
The process of exlraclion oJ melqlr b, electrollsis of
their fkted sa s is called elcaromaallurg. In thlt
process, eleclrons seme &r the reducin? aqent.
Some common methods used for refining of
metals are discussed below:
(i) Electrolysis of NaCl. The s-block ele-
ments, i.e., alkali (group 1) and alkaline earth 1. Distillatlon Process, This method is
employed for purtification of volatile metals like
materials (group 2) which occur as chlorides or
trxosalts are converted into their chlorides. When
electric current is passcd through a fused chloride,
metal (M't+) ions are discharged at cathode and
deposited. Similarly during the electrolysis ofbrinc
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'10/16 Pratlea p's Net4 Course ChemistrqtrfrlD
it used for
2. Liquation Ptocess. This mcthod ing hearth of a reverberatory furnace (Fig. 10.9)
puifrcstion of such metal,' as corttoin nPuities when the metal melts and flows down into the
which are less fusible lhan thc,ncldls tlrcmselves, i.e., receiver leaving the infusible impurities on the
lhe meltingpoinls those hearth. Metals like tin atd lead are pttrified by this
ol tlrc impwities. in ao method.
inert atmosphere sloP-
3. Oxidation Process' Iftis Process of metal melted and a hot blast of air is passed through it
when impurities are oxidised. Pig iron and copper
R
are purified by this method.
EE
Another converter vrhich has been used is
AR
with air. The impurities are oxidised and form a is forced into the molten crude metal through
S
it is skimmed off. Sometimes the oxide of the metal occurs and the heat thus evolved raises the
IIT
itself is added which supplies the necessary orygen temperature to about 2673 K.
to the impurities for oxidation. For example, iron
oxide is added to molteu steel and copper oxide to
(ii)
Cupellation. This method is aPPlied
when the impure metal contsins imPuitiesololher
molten copper. The various oxidation Processes
employed for different metals are briefly described metals which form volstile oxides. For example,
below : last traces of Iead are removed from silver by this
process.
(i) Bessemerisation. This process is carried
out in a specially designed furnace called a be- A cupel is an oval shaped pan with shallow
ssemer converter (Fig. 10.10). The impure metal is hearth and made up of bone ash or cement. The
impure metal is heated in a cupel in presence of
a blast of air or orygen. The impurities are con-
verted into their volatile oxides which escape
along with the blast of air or orygen while the
pure metal is left behind. Thus, when impure
silver containing lead as impurity is heated in a
cupel along with a blast of air, lead is oxidised to
litharge (PbO) which being volatile escapes
alongwith the blast while the shining mass of
silver remains in the cupel.
(iii) Politg.This method is employed when the
crude metal contains impuities ol the oxide of lhe
metal itself. For example, impure copper contains
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PRINCIPLES ANO PROCESSES OF EXTRACTION OF ELEI\,4ENTS 10117
crrzo and impure tin contaiqs stannic oxide The net result is the transfer of pure metal
(SnOr). from the anode to the cathode. The voltage applied
the metal usually a double salt of the rnetal. Wheo metal crytstallises out of the melt whereas the im-
C
electric curreut is passed, metal ions from the purities pass into the adjaceDt molten zone. This
S
electrolyte are deposited at the cathodein the form process is repeated several times till the impurities
N
of pure oetal while ar equivalent arnount of metal are completely driven to one end of the rod which
IA
dissolves from the anode and goes into the is then cut off and d kcarded. The pmcess is usaally
IIT
electrolyte solution as metal ions. The process takes canied out in an inen atmosphete to prevent tie
place as under :
MOLTEN ZONE
t----- I ---+---------->--------.------->--------.>
DIRECTION OF MOVEMENT
t OF I'OLTEN ZONE
MOVING AND IMPURITIES
CIRCULAR
HEATER
ment to be
technology. In this method, zirconium is heatsd
IA
in iodine vapours at about 870 K to form volatile A flow-sheet diagram of the metallurgical
IIT
pure zirconium.
Thermodynamic aspects ofthe reactions uscd
K t7o
'Zr (s) + 2lr(g)--' hlq G)
m15K in metallurgical operations are very important.
These canhelp in decidingthe temperature and the
(l^p*) e2rap-o) Tungstcn filamcnt choice of the reducing agents in the reduction
Z.r (s) + zlr(g) processes. An important thermodynamic functior
(Pw.\ is the standard Gibb's energy change (AG'). lt is
related to cnthalpy and entropy of the system by the
Similarly, - relation,
523K 1700 K AG=AH+AS.
r(s)+zr2(s) ----+ rillG) ------' !(s) +zIzG)
(Inpoe') (P&) For determining the feasibility of aay process'
AG should be negative. Therefore, AG decides the
7. Chromatographlc method. This method is direction of the process at constant temperature
based upon the principle that vadous comPonenls and pressure. We shall learn more about AG and
of a mirture are adsolbed to difrerunt dents on an its applications in class XII.
iborbert. In column chromatograPhy, an adsor-
bent such as AlrO, is packed ia a glass colurm. The
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PBINCIPLES AND PHOCESSES OF EXTBACTION OF ELEMENTS 10/19
Step 1
Slep 2
e Lhu.ton
r- Pollng
R c- El.cEo-I.fnlng
EE
Step 5 G Zone rolining
€ \Apour ph63e rafnhg
AR
olh6r €lem6nts)
S
N
IA
IIT
FIGURE 10.13. Flow-sheet diagram for general mutallurgical operations. In the above diagram,
functions oI the proce-sse-s are given on the left wfiite the methods used are written on the right
R
Q. I . \4,hy ls Fe an abundrtrt element on earth and why sre the elemerts with high stornlc numhers increosingly
rare ?
EE
(N.C.E.R.T.)
AR
Ans. Fe b€cause ofits high nuclear bindinS ener$/ is very stable and henc€ is an abundant element on the earth. As
thc atomic numbei increases, the niutron/proton, ie., n/p ratio increases. As a result, the Duclear binding
C
enersr decreases aod hence the abundaoc€ of elemeots with high atomic numbers decreases.
S
Q. 2. Give e'omples oflgncous rnd sedim€rtary rcck& What l9 rhe origin ollgneous rocks oDd
what is the origitr of
N
IA
scdiEentary rods ?
IIT
Q. 5. Copper and sllverlie below ln the electrochemical serics and yet they sr€ found in the combined state 8s sulphides
ln nsturq comment (N'c'EJ.n
Ans. As exptai[ed in Q. 3, due to high polarising power of their cstions, their sulphidcs arc eveD more s]able than
the metals.
Q.6. Metal,s usuolly do notoctur ln n turt rs nltrst4s. why ?
Ans. Nitrates of all metals are solublc in wBter. Thcreforc, if metal dirates were Present in the crust of earth, ihes€
would be slowly and graduallywashed by rain wster into thesea. It is becauseofthis reason tbat metals usually
do not occur iD nature as nitrates.
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PBINCIPLES AND PHOCESSES OF EXTRACTION OF ELEMENTS 1O121
Q. 7 . How does NoCN oct as a depEssont h prcventing ZrS ltoE folmiDg the ftoth ? (N-C-E.R,T)
Ars. NaCN combineswith ZnS to form a complex, Na2 [Zn(CN)4|on the surface of ZnS aDd thus prevenls it tiom
forming tbe froth.
ZnS +4NaCN .+ NE[ZD(CN)4] + NazS
Sod. tclracranozimarc (lI)
Q. 8. Wby b ltadvontogeous to rEst $llphlde orc no ttie dide befotr rEduction ?
a (N.C.E.R.T)
Ans' The standard free energies (Ac') of formatioo of most of the sulphides are greater than those of CS2 and
H2S (CS2 is, iD fact, is an endothermic mmpound). Therefore, neither carbon nor hydrogen can reduce Detal
sulPhidcs to metal. Io coDtrast, the staDdard free energies of formation of oxides are much lower than ihose
ofS02 and heDcr csidation of metal sulphides to metal oddes is thermodrramically favourable. Therefore, it
is the mmmon practice to roasr sulphide ore to the oxide before reduction.
Q. 9. !,r/het is ahe themod5mamic consideration in the choice ofo rcduclng [gent in met{llurfs/ ? (N.C.E.R.T\
Ars. For aoy spontaneous reaction, the free enerry change (AG) must be negative
Ac =AH -TAS
AH is thc enthalpychangc, during rhe reactioD, T
is the ab6olute tempcrature and AS is rhe change
in entropy duriDg the reacrion.
Let us investigalc the AG during lhe conversioD
of a metal i[to its oxide
M+02 MO2
- L
In this reaction, dimygen---a gas
is us€d up, and E R
EE
metal oxide-a solid is formed. Since gases have f
higher entropy than liquidsand solids, therefore,
o
AR
,E
temperonre.
IIT
Ans.
IIT
anbdrousbyheztinsinacurrentofHclge6.Theanh}drousMgcl2thusobtaiDedisaddedtoamirureofmolten
NaO aDd CaCl2 (93-1025 K) and electrobsed when pure Mg gets dePosited on the caihode
(iii) Rare earth metals (ie., lanthanides abbrwiated as Ln) can of
ch
it tiiirimpl" tuttt tr"h ai niirates, sulphates, bromales, P€rchlora
r.lg(No3)2 . 2a H2ct because they crystallize we
to
in 1lbr1, . :
"t a numbcr
Lu, therefore, salts at the Lu eDd of the Series will crystallize first. The Proc€ss has to be reP€ated
to good separations. Non-aqueous solventssuch as diethylether have Jeenused to seParate
ofiimes o6tain
Nd (No3)3 and Pr (No3)3.
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PHINCIPLES ANO PROCESSES OF EXTRACTION OF
ELEMENTS 10123
Q. 1. Whot is a
mineral ? How doqs it dilfer from an ore?
Ans. The natural materials or the chemical compouDds iD
wbich the metals oc€ur iD the earth are callcd mioerals.
The minerar from which the me."r is convdnientry ano economicaif,liiieo
are minerals bw all minerols ore nol ores.
i" *,ea ,n_o rc. -fht)s, alr orer
proccss.
Q. 6, What is gangue ?
N
IA
Q. 9, Deline aluminothermy,
Ans, The reduction of oxides of metals like CrrOr, Fe2Ol,
MDtOa etc. to rheir me.ols by alun,niunt is called
aluntinothermy.
Q. 10. WhEt is cupellatlon ?
Ans' cupellation is a method used for relining ofsuch nretals which
coDtain impurities otother metals which rorm
volatile oxides. For example removal oflast traces of
lt from e!.
Q. I l What is potirg ?
Ans' PoliDS is a method used for refininS ofsuch meials which
contain impurity of the oxidc of the nretal rtseI. For
example, CUO in crude Cu.
Q. 12. WhEt is th€ principle ofzone reliring ?
Ars. When the molten solution o[ ito In]pure rDetal is allowed to cool, thc purc melal cr]stallizes
impuri es remain i,, solrtion. out whilc the
Q. 13. What is Vnn Arkel method ofobtaining ultrapure metals ?
Ans' The impure metal('Il or zo is first converted inro irs volalile
iodide by hearingwith 12 at some low temperature
and then decomposing the voratirc iodide at a suilabre
high tcmperature to give the pure metar. For exampre.
870K _- 2075K
(Inpurc) w ril"n.nr 1rr).i - ''
Q. 14. Glye ihe chemical formula ofdolomite and cornalllte.
Ans" CaCOr.MgCO3 and KCt.MgCt2.6H?O.
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P ratl e a lr's N eut Coiise Chemist,AifrlD)
tol24
Q. 15. GiYc one imPoitsnt ore ofal$miniunr'
Ans. tJauxite (Al2O3 . 2H2O).
Ans'
Q. 16.
iaB':[iH:flf:'lliffiill;f,"",*3,)"li
elrts it fron] formin8 the froth'
R
EE
Question
AR
is different'
Sec. 10.1. 1. Explain uhy terrcstiat aDd cosnic abundance ofelemeots
C
to 10.6.
why are the elements with higher atomic Dumbers
S
increasingly rare ?
IA
organFm
4. Name a few elements present in lhe livtng
of tbe various elements present in ihe sea- water'
5. Givg a brief accouDt
6. Ocean is a storehouse of the clements Colnment 'l
yet only a few elements are recoveted from it
Although sea water contains almost all thc elements'
E. How d6 the elements ocrur in nature
?
Sec. I0,7'
to 10.10. 9. fi;;;;-r;;i;"r""ts occur in the Dative state whilc others do oot ?
10. Differentiate betweeD mineral and
ores'
predict the mode of occurreoce o[ the following three types of metals : (i) Highly
reactt-: q'j']:)
13.
i,iftloo";,;,y;;;,iliie.,i:e) (iii) noure nritarlr:e,eu; N'c'D'R'r)
t4, Howdonon-metalsoccurinnature?Howaretheyextracted/isolatedfromtheirDaturalsources?
(N.C.E.R.T)
Sec.l0.l0. DiscusssomeofthefactorswhichncedconsidcrationbeforedecidingoDthemethodofgxtractionof
(N'C'E'RT)
to 10,12. metal fronr its ore
What is the role of a stabilizer and of a depressant ?
16. Describe the principle of froth flotation Process (IVCE R'I)
Give oDe examPle each. ?
by froth flotation proc€ss wbat is meant by a dePressaDt
17. Name three ores which are concentrated (N.C.E.R.Tl
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PFIINCIPLES AND PBOCESSES OF EXTRACTION
OF ELEMENTS
10125
18. Differentiate betweeo the followin!: fi\ calcinatioD .., .^^.ll-l_.ll]-
*r.t.,,ri^" and roastiDg' (ri) gaDgue aod flux'
r9. whar is meanr by *r""rorrion J8;":)
20. What is the purpose ofroastiDg and calclnation
ln meEllurgical operations I
21. What do you mcan by leaching ? Fxplain with
an cxaD.rple.
22. Explain rhe difference between leaching and levigation.
23. Silver ores and native gold have to be leached with metalcyanides.
Suggesr a reasoD for this.
24. Giviog ooe example in each caje, dittereniiate between
(i) Hydrometa urgy and (ii) Etecrromera urtl/
25. What is a flux ? Discuss its types and uses in ntetallurgical
oprations.
26. is aluntinothermy ? Explain wth one example-
27. _What
What do you uoderstand by lhe following terms
?
(i) Roasring (ri) Catcination (ir) Snrelting.
2t' Naore rhe nretars which are associated wirh rhe
forowing rerms in their exrracur, ,r.,, ,$l;"';X
(r) Bessenter,s converter (ti) Blast furnace l'
(ru) A.luntiriothermic process (iv) MagDetic
separation
,r. I:.!1* gl" leducing agent rDa p€rlicular case depcnds upon rhe the
you agree with this statement ? rmodyoam- r",$.?'J;11
I
30. rscarboDasarisro"to.y,.ou"r,,g'ffii#l;Hffi'::;Hi',?;," (N.c.E.R.r)
3L Describe rhe principrcofeach olr the follo\ring
rns (N'C-E.R.T')
34.
S
36. ^ WC.E.R.T)
J7.
Sreet Aulhoriry of India. W.C.E.R.T)
Cupeltation.
3t. d c€lcination ?
39. and poting ?
werQueeti
Sec. 10.I. L Discus the origin of elementr iE rhis unryerse.
to 10.t. Dtsclss briefly ttrc distribution ofclemcnts
on eanh.
3. Wtite the zones of the e3rth and discuss the
distributioo of clerEat! iD thcse zoncs.
4.
tioll of thc earth.
Scc 10.9. were they formcd duriog formation ofe€rth
6. ?
to 10.12. ores,. D€scribe bricny the various methods
used for
Giye a bdef account of tbe various methods
used for obtaining mefals from tbc
r@$ed or calcjtred
? Describe bricrlv thevariousrErhods empgrcd
YJHt,f#:1'iifl.?:fl:rry turisohtionormctars
9. Give an appraisal of the methods uscd for
rcduclion of mctallic qidcs to mctals.
10. Discuss briefly the various methods us€d for
refioing of crude metals.
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,.."l.J.....i,r...'.,Jt.i.i,.rr,.,,
inc
thin i,[il
S
rJJsffi::?il::l
N
easi
IA
e to tho roller'
not
IIT
ro/26
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PR!NCIPLES AND PBOCESSES OF EXTRACTION
OF ELEMENTS 'tol27
15. Malachite
(a) Iron (b) Tinc Roasted gold ore + cN - + H2O --; lxl + oH-
C
(M.lPM.T 1998)
IdeDtiry rhe comPlexes [Xl and [Yl
N
found
IA
native in nature ?
(a) A.luminium (r) Copper (b) x = tAu(cN)4r2-, Y = [zn(cN)a]2-
(c) Iron (d) Magnesium.
(;t1.PC-E.l:. 1999) (c)x = [Au(cN)2]-, Y = [Zn(cN)6]1-
17. Which of the follo 'ing metals is n]ost abundaflt in (d)x = {Au(cN)al-, Y = lzD(cN)412-
'l
the earth's crust i.l T.2l)0.1)
(a) Me (b) Na
25. The olethod of zone refining of metals is based on
(c) Aj (d) Fe ( teee)
the PrinciPle of
(a) ireater mobility of the Pure metal than
that of
Hearing Pyrites to remove sulphur
is
l&
(a) Smelting (D) Calcination the imPuritY.
lhat
(c) Uquarioo (d) Roasting. (b) higher melling Point ot thc imPurity than
t itl.l: llil. l: 200t) ) of the Pure metal.
tban
c,lrPel- (c) Ereater noble character of the solid metal
19. In the metaltursr ofwhich of the fottoxinS' that of the imPuritY'
lation Process is us€d ?
molten
(ll rrcaler solubility of the imPurily in the
(a) CrPPer ;late rhan in the s( lid.
(c) Iror t(R \ t' l!rl.'l:2A01)
\.1 tL.h:.L.200J
(c) Fe (d) Cu Ouittt.c. zoot:
C
HlNT5./EXPLANATIONS to
S
7.
IA
Fluorspar is CaF2.
:8. Calcium phosphate is calicd Tho-as stag.
IIT
9. All nitrates are soluble iD water. J3. Since the reduclion potetrlial of Mg2+ (_2.3-t
V)
ll- much tower than rhar ofI{rO
1_1t.6i yy,16s1"1
rs
Silver dissolves in NaCN solution.
16. Copper Iore, H2O gets reducerl inprefereneof Mgz+ ions.
is very slowly a
acked by air, ntoisture and
COz and henc.€ sometimes occurs in nalive state. J4. Ore particles float because lheir surfacc it wctted
by oil.
ADDITIONAL UESTIONS
The lollorlng
key to choosJ 2' U3€ atle fotloryin8
(a) Ifboth assertion ard resson are CORR-ECI
and reasou is the CORRECT explanation ofahc
assertion.
(b) If hoth o.sertioD and ,"asor orc coRREq but
rcasor ls Nor the coRREcr exptsnatron of the assertion,
(c) If assertior is CORR.ECI, but reason is INCORRECT
(d) Ifassertion is INCORREC,I; bur reason is
CORRECT,
L.LI E R .S
26. a 27. tl 2a. b 31.d 32. b 33. d 34. b 35. o
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10/30
l) Reflson (Cohtmn 2)
Assertion (Column
1. 'Il can be Purified by van Arkel Process' lll1is a rolarile coln=-und
whhhdcq]nrpces at a high lemp€rature
has a high nleltiDg Polnt'
2. Aluminothermy is used for exkaction of Alumina
chromium from chromiun] oxide'
associated with these ores dissolve io NaCN
A! aod Au are extracted by leaching thier I$purities
o; with a dilutc solulion of NaCN' ln fro(h-floatation process Pine oil is used because
it preferentially
C.arboDates and hydroxide ores are con'
wets the ore
centrated by froth lloatatioD process' Particles-
TruelFalee ?tatemente
o'td 4. The process emPloyed lo conceotrate an ore is
Which of ,he Jollo,iing stalefienl\ are true called (he
-
s. ieactring Particular mioeral
1.
io un orj ivelY bY using cer'
taiD acids, bases or other reagcnts'
e. freiim&al orirnpurities ftom an ore by forming
salts is called slaSSing oPeratio['
,l ieactive cannot be obtained
z. ia"iar. tntria
",Jiigfily
by elecrolYtic rcduction.
called an ore.
FilllnThe Olanks metals are
exkacted Highty eleotroPositive metals like alkali
1. AD orc is a . . .. from which the metal ca n be
2.
ies 5.
R
EE
6.
'io ;;
AR
3. its ores.
orrvert it into ....
Vatchin7TY?e Q.uesAions
C
S
5. concentatioD of ore
rn Colun]n B. od
IIT
6. Sodium chloride
Column A Column B is used in
7. Sodium bicarbonate
l. Bauxite (a) Flame to.st
8. Alkali metals aro
(b) r-Block elements (i) An ore ofsodium
2. Galena 9 Atka[ne earlh metals are
AlkaliDetals are extraoted bY (c) Frolh-floalalion 10. Magnesium does nor give (/) Pbs
3.
:iii
MENTS
'Iiue 7' Blse'
, mineral 4' Tiuc 5' 'Iiue 6'
FILL IN THE BLANKS
H>/d?ogen
:lXii
'iEi ' ,.lJ,.*
Unique position in the periodic table, occurrence, isotopes.
i Dihydrogen-preparation (including commercial preparation), properties, reactions and uses.
ii Hydrides-molecular,salineand interstitial.
i: Water : structure and aggregation of water molecules, physical and chemieal properties, hard and r:
ii soft wate4 water softener. Heavy water, hydrogen peroxide. hydrogen economy, use of liquid i
i1 hydrogen as a fuel.
R
EE
AR
C
Heprepareql
IA
could not be
eet's periodic
ble because of
The various forms 'isotopes, allotropes, (i) In some properties, it resembles alkali me-
molecular and ionic forms are hydrogen are given tak. as such, it b" placed in group 1 of the
in the box below : "unwith alkali m--e1[l-s:
periodic table along
Erectronic
Lrvvrrvtrtw : lsr
lf ,i -"lij1):,::.:ilil
g oup 17 along with -:i.^::::'
" wq' uv
halogens.
configuration
L(ltllSul dLlull
Isotopes : prorium, IFI r...
(irr) fn:oT"y,:tanotherprop,erties,hydrogen
ditfercfrom-both a]kali m-elals and [alqgggg.
Deuterium, 2H or D I position of hydrogen in theperiodic
Ttirium, 3H or T I ., is controveglg!3r orygll$ous, The main
lhus'th.1
: a_Lr
orthohvdrogen'o-H, I -table
iAltotropes
:
rrrrhnhrnrrnoen
I
Parahydrogen,p-H, p"ir",..r"r#r#ffihffith"".rffi*
iril;;Ji;l;;;;;;;;t;;fr'y di,Z;.;J betow :
tur
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11/2 Pradeep's
l. Electronic configurati(,n. Likc alkuli me- and thus have one eledron le.ss than the stable
tals. hydiogen also conlains one elcclron in its out- configuration of the nearest inert gas. Hydrogen, on
ermost (ualence) shell : the other han( has one electron in the outermost
Hydrogen, H Lithium, Li shell and thus has one electron less than the stable
1sl "ll
zst configuration of the nearest inert gas, l'.e., He.
Sodium, Na Potassium, K H One elcctron less than Hc
Lt2 zt2 2po 3st L\2 L2 476 7.\2 3p6 4st Lyl b2
2. Electropositive character. Like alkali mc- F ()nc electron less than Ne
tals. hydrogcn also loses its only clectron to lorm
hydrogen ion, i.c., H+ Qrroton). 1s2 z\2 2ps t"2 %' zpo
H+H++r Cl One electron less than Ar
lrl Iro 1s2 zsz 2p6 kz 3ps ltz N2 2p6 k2 3p6.
Na Na+ + s- 2. Electronegatiye character. Halogers have a
ls' 2sz 2p6 !s1 1s2 2$2 zp5
strong tendeocy to gain one electr'on to form halide
Tltus, hydrogen like alkqli metals Lltltibitli
ions. In a similar way, hydrogen shows some tendency
c le c t rcpos i tiye cha rq cter.
to gain one electron to form hydride (H-) ion.
l-.Oxidation slate- Like alhali metals, hydrogen
exhibits an oxidation state of + [ in its compounds. H + r- ------------) H-
H+ cl- Na+ Cl- K+ Br- h'l 1.r2
Hydrogen chloridc Sodium chlodde Potassium broDide (He gas conliguration)
4. Combination with electmn€gative elements cl +c- +
ornon-meia.ls. Like alkali metats, hydrogen combines
cl-
k2
with electronegative elements (non-rncrals) such zr^s Lt2 zr2 2p6
R 3ps ts2 zt2 2p6 3s2 3p6
EE
orygen, halogens and sulphur forming their oxides, (Ar gas cortfiguatiort)
halides .rnd sulphides raspectively. For example,
AR
Halid.es :HCI like NaCl, KCI etc. halogens but much higher than those ol alkali metuls.
S
Sulphide :
HrS like NqS , IlS etc. ElcDlcnt lonizqtion enew
N
IA
II.
Resemblance with Halogens. Hydrogen At utrcde At cathode
resembles halogens, r'.e. f;, Cl, Br and I ofgroup 17 Electrolvsis
of the periodic table in the following respects :
2NaH(/) ..................- HzG) + 2Na(/)
1. Elcdonic configuration : All the halogens Elcctrolysis
haw seltn electrons in their respedive outcrmost shells
2\l('l(/) .+ Cl2G) + 2Na(/)
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HYDBOGEN 1113
6. Atomicity and non-metallic character. Just rutcleus and only one electron in tlu extravcleor
likc halogens, hydrogen also exists as a diatomic Paft.
nrolecule : Hz,F2 , C\, Br2 etc. Furthcr, like 3. Nature of oxides. The oature of oxides of
halogens, hydrogen Ls also a tlpical non-ruetal. alkali metals, halogens and hydrogen is quite dif-
7. Combination with metals. Hydrogen com- ferenl. The oxides of alkali metalt qre basic while
bines with highly electropositive alkali trnd alkalirc those of halogens are a.ci.lic but the ox(,lc of
carth metals to form metallic hydrides. In a similar nyarogei, i.e., Ft ,o is neutral. Thus,
way, halogens combine with these metals to form HzO ,
LirO , NarO . K2( ) etc , Cl2( )7
metallic halides. Na&al --v- Acidic
Bosic
Wth alkali metals
zNa + t! -._ 2NaH 4. Absence of unshared pairs of elc,Ltrons.
---
The hydrogen atoms in hydrogen molecule do not
2Na + Clz + 2NaCl possess ary unshared pairs of electrons whereas
With qlkaline earth metals halogen atoms in halogen molecule possess three
unshared pairs of electrons as shown below :
Ca + H2 CaI{2
+ Cl2 -+
Ca CaCL HH CI CI
ll. Formation --r
of coval€nt compounds. Lile
halogens, hydrogen readily combhes with non-mo- 5. Nature of compounds. The compounds oI
tals such as carbon, silicon, nitrogen etc. to form hydrogen with halogans, i.e. hydrogen halides (Hf,
covalent compounds. HCl, HBr, Hl) arc low boilirtg covqlent cotnounds
With hydrogen : CH4 siH4 NH: whereas alkati metal halidcs (Lif; NaCl, KBr, CsI)
R
arc high melting ionic soli^.
EE
Methane Silane Ammonia
: CCl4 SiCl4 NCl3 6. Size of ions. The size of H+ ions
AR
With halogens
( - 1 -5 x lO-3 pm) is much smallor than those of
Ca6on Silicon Nitrogen
C
letrachloide tetrachlondc trichloridc alkali metals. Similarly, thc sizc o[ H- ions (220
S
rcplaced by halogens and halogens can be replaced aqueous solution as hydraled pruton having the
IIT
by hydrogen. For example, formula. IHe( )ol+ in which four Hr( ) molecules are
Diffuscd sunlight
cHl + cl2 ---------------- cH3cl + HCI tetrahedrally arrangcd around the H+ ion. How-
ever, it is generally rvritten as [H.o+l and called
Mcthane Mcth,l
chloride hydronium ion. Alkali metal cations also exist as
Sn/HCl hydrates but the extent of hydration decreatses as
cH3cl + 2[Hl ....._ cHl + HCI the size of alkali metal cation increases. Thus
Methyl or Z^/HCI Merhane
chloride
H
lII. Difference from Alkali Metals and
o ._Ht
H
Halogens. Hydrogen differs from both alkali metals
irnd halogens in the following respects :
t. Hydrogen is comparatively less electropo:;i-
tive thqn qlkqli ,netals and less electronegative thdn lL(Hro)61+
f,ilhium hcxahldrate catlofl
hologens.For example, hydrogen has less tendsncy
to form H+ ions as compare dto alkali metalswhich Halide ion-s, also exist in aqueous solutions as
rcadily fbrm monovalent cations. Similarly, hydrated ions but their structures are not well es-
hydrogen has less tendency to form H- ions as tablished. That is why, they are usually represented
compared to halogens which readily form halide as X-(ag) where X =F,Cl,Brorl.
(X-) ions. Conclusion. From the above discussion, it fol
2. Unlike lulogens attd alkali metals, lrydrogen lows that hydrogen is unique in its bchaviour be-
contains otb) one proton (bfi no rtetLtrons) in its cause it
not only resembles alkali metals and
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1114 Neta Course Chent i strg
halogens in certain properties but at the same time Tiitium being unstable because of its radioactive
it differs from both of themin certain other proper- nature occurs only in traces (one in l0l8 parts) i.e.
ties. Therefore, it is not justified to include the natural abundanccs of lH, lH.andfH arc in the
hydrogen either along with alkali metals ol Wup I ot ratio of1:1.56 x 10-2: I x 10-18.
halogens of group 17 In other words, /r e position ol
hydrogen in the peiodic table is qnomalous or con-
Some importalt characteristics of thesc
isotopes are giveD io Table 11.1.
fioversiol. That is why hydrogen is sometimes
referred to as a 'ro8u e element'. TAIILE 1Lf. Atomic I)toperties
')f lsotr)prs
rrl H.r,rlrogen
1 1 3. Occurrence of Hydrogen :':r:.": :::1:. :
Property II I) I
Hydrogen is the most abundant elementin the .007825
Relative 1 2.014l(D 3 016049
univerce (70Vo of the total mass of the universe). atomic mass
The giant planets such as Jupiter and Saturn con-
Nuclear spin 1 1t2
tain mostly hydrogen. Hydrogetr mnstitutes about
quantum
half of the mass of the sun and stars.
number
The extremely high temperature of the sun NoD-radio-
Radioactive NoD-radio- Iladioactive,
brings about fusion of hydrogen atoms liberating stability active stable active stable emits low
large amount of energy energyP-
4 ------*
lH lHe + z\e + Energy particlcs,
Helium Positon tr,tz= 12 33Y
It is the third most abundant element on the Electronic structure.All the three isotopes of
surface of the globe. In the combined form, it con- R
hydrogen have the same atomic number (Z = 1),
EE
stitutes 15 47o of the earth's crust and the oceans. therefore, all have only one electron in thcir only
However, on the earth, it, is the Dinth element in shell (i.e., K-shell) and one proton in the nucleus.
AR
order of abundarce and forms 0.97o of the earth's Since the mass numbers of the three isotopcs are
crust by weight. In the crustal rocks, it is 10th in
C
matter.
Earth does not possess enough gravitational
pull to retain the light H, molecules, therefore, it is
not found in our atmosphere.
1 1.4. lsotopes of Hydrogen iiii::ri:i::i:i:i:,i1i::::.,,:i:!rri:r:: i:,:, i
Hydrogen has three isotopes. These are called FIGURE I l.l. Isotopes of Hydrogen
protium, d€uterium and tritium.
Represenlation. The isotopes of an clement (i) Protium or ordinary hydrog€n [lH]. This
are usually represented byputting the atomic num- is the most abundant isotope ofhydrogen. Since its
ber as the subscript and their mass number as the atomic number is 1a-nd mass number is also 1, its
superscript on the symbol ofthe element. Thus, the nucleus has only one prolon (but no ,rcutron) a\d
three isotopes of hydrogen are reprcsented as one electron is revolving around the nucleus in its
lu, ]u or o and fH or T, only shell, i.e. K-shell.
Occurrence. The most abundant isotope of (ii) Deuterium or heavy hydrogen t fH or Dl,
hydrogeu is protium. This occurs in natural Its natural abundance is 0.O756% . It is usually
hydrogen to an extert of99 9844Vo;the remaining prepared by the electrolysis of heary water (DrO).
0.0156% being deuterium mostly in form of HD. Since its atomic number is 1 and its mass number is
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HYDROGEN 1 1/5
2, therefore, its nucleus has one ptoton snd one Properties- lsotope Elfect. Since the thrce
neutron w[)le on,e electron is present in the K-shell. isotopes ofhydrogen have the same atomic number
It is generally denoted by the symbol D. and electronic configuration (Lrl), they have
Qii) Thitium tfH or q.
It is the least abun- similar chemical properties. But owing to their dif-
dart (Lo-167o) of all the isotopes of hydrogen and lerent masses, the rates or equilibrium constants of
is forrned in the upper atmosphere by reactions thesc reactions aie different, For example, reaction
induced by cosmic rays.ltisrodioactive with a short between protium and chlorine is 13.4 times faster
halfJife of 12.33years.It decays byB-emission with lhcn bclween deuterium and chlorinc : protium is
no 7-radiations adsorbed more rapidlythan deuterium on activated
+ charcoal. Similarly, electrolysis of ordinary water
?H ------ lHe _[e
(HrO) occurs more rapidly than thaI ofheary water
It is prepared artificially by the bombardment
(Dzo).
of nitrogen or an isotope oflithium with neutrons:
]aN + ln
_.....- lrc + iH Thit ttpeolilifrerenceifiprary h dw todlfferenra
jI-i + &, -----------
lne + fn in atomic mds.scs is cal*d lsotope tffect.
Since its mass number is 3 and atomicnumber Further, due to different masses, the physical
is l, its nucleus has one proton ond two neutrons propertics of these isotopes are quite different.
while one electron is present in the K-shell. It is Some common physical properties of H,
usually represented by the symbol T. (dihydrogcn), D, (dideuterium) and T2 (ditritium)
nMs, the tlvee isotopes of hydrogen differfrom are given in Table 11.2.
one another only in the numbet of neutrons i,t the
nucleus. R
EE
AR
TABLI
C
Uses of Thitium. Tiitium is used to make ther- I. From water. Dihydrogen may be obtained
monuclear devices and fbr carrying out researches from water by any of the following method.s :
in lusion reactions as a means ofproducing energy. 1. By the action ofwater on metals
Tritium gas is usually stored by making UTr, which (i) Cold water Very active metaLs, l'.e., alkali
on heating to 673 K releases Tr. and certain alkaline earth metals like Na, K Ca etc.
671K react with water at room temperature evolving
zuT, 2u +3'f2 dihydrogon.
It -
widely used as a radioactive tacer si\ce
is ia 2Na + 2H2O ......._ 2NaOH * H,
is relatively cheap and easy to work with. 2K + 2HrO -----------+ 2KOH + H2
i1 t n!^Drralron or Dihydroggn
Ca * 2HrO ......._ Ca(OH)z + Hz
The important sources of dihydrogen are The reaction with alkali metals is so vigorous
water, alkalies arrd acids. and exothermic that the hydrogen evolved catches
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1 1/6 Pradeep's
(iii) Steom. Still less reactive metals likc Fc, Fe + 2HCl -----------+
- FeCl, * H2
Sn, Ni etc. dccompose steam at high temperatures Mg + 2HCl ----------- MgCl, + H,
evolving dihydrogcn.
3Fe+ 4H2() .....-.-.- FerOo * 4H, Metals like copper, silver, mercury etc. which
are less electropmitive than hydrogen (i.e., lie
(Stea,n) Magnetic oxide
R
below hydrogen in the electrochemical series) do
EE
2. Byelectrolysis ofwater, Dihydrogen of high not liberate dihydrogen from acids.
purity is usually obtaincd by the electrolysis of
115.1. Laboratory PreParation
AR
of
watcr in presencc o[ small amount of an acid or a
Dihydrogen
C
shorvn bslow:
IA
2 2H2@) OzG)
Granulated pieces of zinc are placed in a
Pure water is only weakly ionized (i.e. is a bad Woulfe's bottle and are covered with water. The
conductor oI elcctricity) but in presence of an acid bottle is fitted with a thisde funnel and a delivery
or u base, the degrec of ionization increases. tube as shown in Fig. 11.2.
H2t)(/) ---------"r H+ (aq) + OH- (aq)
Atcothode: H+(aq) + c- H
FI, + .H - HZG)
Atanode: OH @q) + - OH+e
2H2O(t) + O2@)
on magnesium ribbon. hot iron. The method, in fact, consisls of two stages.
Mg + HrSOn (dil.) ......._ MgSOn + H, (i)
IIT
(Uyeno's method),
Similarly,
Ni- Cr
QH, G) + 3 H2o G) -.........- 3 co (s) + 7 itr(S)
DIOXYGEN<- .---} DIHYDROGEN 1270K
trI C(s) + HrO
127C K
C(s) + H,@)
R
CO is converted to CO, by passing the gases
EE
and steam over an iron oxide or cobalt oxide
AR
.
IA
673 K
FIGURE 11.4. Eectrolysis of water for commerciat This is called the water gas shlft rraction.
IIT
prcparation of dihydrogen.
small amounts of dihydrogen (l
ln this cell, iron sheet is used as a cathode -Relatively
l7 m3h-r) are obtained by passing a 1 :-1 molar
-
while nickel plated iron sheet acts as anode. mixture of vapourised methanol and water over a
base-metal chromite q.pe catsl',st at 673 K. Thc
mixture of hydrogen aud carbon monoxide thus
obtained is made to react with steam to give CO,
and more dihydrogen
673 K
NaOH solutionis used for electrolysis, the decom- CH3OH--.............* CO + H2
position of water takes place as follows : Catallst
H2O -.........- H+ + OH- 673K
CO + H2O ....-........r COz+Hz
At cathode, Catatyst
H+* e- ........-.- H. 5. As ! by-product. Large quaotities.of
dihydrogen are obtained as a by-product in various
H2
industries. For example,
At anode, O From petroleum cracking planls,
4OH- + 4OH + 4e- (ii) Manufacture of sodium hydroxide by brine
4OH + electrolysis, (iri) From coke oven gas.
2 HzO + 02 (u) Ttermal cracking of natural gas.
4. From hydrocarbons. One of the most Dihydrogen mayalsobe obtained by thermal crrck-
recent methods developed for manufacture of ing of natural gas.
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HYDROGEN 1l19
lnoK 2. It is the lighest substarre known. For ex-
CH1 """""""'- C+ zHz
ample, one litre of dihydrogen at N.TP weighs
catallst
0'0899 g. Its densityis approx. U14 th ofthat ofair.
Presently above 77Va of the industrial
hydrogen is produced from petrochernicals, 187o 3. It is slightly soluble in water since its
from coal, 4Vo from electtolysis of aqueous solu- molecules are non- polar.
tions and l7o from other sources. 4. It can be liquefied uDder low temperature
and high pressure.
1 1.6. Properties ot Dihydrogen
Some important physical constants of
(d) Physical propertles. l. lt k a colour- dihydrogen alongwith dideuterium aud ditritium
less, tosteless and odourless gas are given in Thble 11.2.
ortho ard Para Hydrogen, Dihydrogen has two nuclear spin isomers called onho and paiOitryorogen.
when two hydrogen atoms combine to form a molecule ofdihydrogeD, the two electrons arways spin
in the
opposite d irections (Part li \ uclution principle) as orhenrise the moteiute wrri not ue sta6e. How&er, the
spins
of the protoDs (nuclei) may either be in the same direction or in the opposite direction.
Wen the spiw of the nuclei are in
the same direction (pnallel spiru),
dilEdrogen it called ortho R
EE
hydtogen and when the spins ore
in rc oppoite dircctioru (at-
AR
nuclearspin = + + 1= nucl€arspn'++-
Conversion of one isomer into the f 11
+=0)
IIT
The reactivity of halogens towards dihydro- of octacarbonyl dicobalt as catalyst under high
IA
S;
IIT
ff,g z. Tlc Dame dibydrogen is commonly used tor H2 molecule, but while referring to the isolopic mixture with
those
isbec
ol lhe metal without disto ing ahe metal lqttice'
R
EE
(iv) Tlrcy hne high melting snd boiling Points
atd conduct ekctricity in the rttsed state' libersling
AR
dihydtogen at he anode.
LaH3,TiH2,Z.rHz, HfH2, vH, VH2, NbH, NbH2,
C
O + e- ""-'' Na (l) t
N
(v) They have high heats of fotmation and are called these hYdrides,
IIT
always stoichionetric.
(vi) Except LiH, they bum in air o', strong #iii:
called
heuting (675-775 K) rfue to heir decomposttion
into hydmgen which is inllammable lnterstitial hydrldes.
615_TEK These interstitial hydrides rnay also be
CalI, """""""" 91 a 1q olid solu-
(vil) rmthe it is trot
ol in the in-
correspon tion
ions with
dihydroge
NaH (s) + HzO (/) ...- NaOH (aq) + H2 G)
delocalized electrons.
Propcrties. Somo imPortant Properties of
CaH2 (s) + 2H2o (l) "+ these hydrides are listed below :
Ca(OH), (aq) + ZHz@) (i) They are hard, hove a metallic lustre, cott'
&rct etectricity and have magnetic properties.
Because 6f the exothsrmic nature of the reac-
tion,(he evolved H, catches fire. The frres so The
(ii) thon
those of mela e the
produccd cannot be extinguished by CO, because crystal lottice
it gets reduced by the hot metal hydride- However,
(r,r)These hYdrides are often nll
sand is useful since it 3 fiighly stable solid.
stolchiometrlc (ZrH, where X : 1 30- 1'7-5,
(iii) Thq arc powerful reducing agenls, espe'
cidlly at high temPemtwes TiH, where X = 18-2 0, ZrH,.o, Pdll6.7,
2CO + NaH I HCOONa + C VHr.6, LaH2.sz, YbHr'55, CeH2.z) Further the
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HYDI]OGEN
11/13
rotio of H-atoms tothe metal atoms in these hvdides 713 K
is not frxed but vuies with the temperature ;nd the Hr(g)+S(/) HrS (g)
Ptefsure. Dark,little moisture
Uses. Due to interstitial hydride formation, H2G) + F2@) - HF(0
these metals absorb large volumis of hydrogen ori 23K
their suytace- This propeny of adsorption of igas by (ii) By reduction of a suitable halide with
u tnetol ir known as occlusion. LiAlHoin dry ether
occluded depends 4 BCl3 +
LiAlHl -....t 2BrHu + 3 AlCl3+3 LiCl
3
te of the metal, r..e.,
SiCla + LiAlHa------- SiH4 + AlCl3 + LiCl
nt > plalinunt >
(iii) By action of acids on suitable binary com_
If red hot Pd is cooled in Hr, it
absorbs or poun^.
occludes about 935 times its own volume ofH, gas. 2 MgrB2 + 4 H3PO. .......;
quite small. Their general formuia is-either XH, 4 AsH3 + 3 H3BO3 + 3 NaOH
S
(for s-block elements) or XHr_, (forp-block ele- Classilication. Depending upoa the number
N
_ _
IA
valence shell.
elecfon-dqcient, elecffon-exact and electron ich
crete covqlent
hy*ides.
wcak van der
are cqlled covalent or molecular hydrldes. _Properties, Some important properties
- of
covalent hydrides are discussed below :
Nom€nclaturc. The systematic names of
molecular hydrides are usually derived from the (r) ually volatile com-
name of the element and the suflu-ane. For ex- pounds ioiiing points and
ample, phosphane for PHr, oxidane for HrO and also do
azane for NHr. However, common names like (ii) Hydrides of gruup lj (i.e. BH,,AW, etc.).
phosphinc, water and ammonia are more common_ do ,tot have sufrcient number of ekclrons to Iomt
ly used. normsl covalent bonds and hence are cslled
electron-defi cient hydrides. They geoerally exist io
_ Preparation. These are preparcd bya number
polyneric forms such as Brtlu, noH,o, 1ntfury, e tc.
ot ditterent methods:
(i) By direct combin&tion of elements with _ (.i0 Hybides tl group t4
CHn, SiHn, GeHo, SnH4, PbHi have exa{t number
0.e.
th lty drogen. For example,
673 K 200 alm of electrons to lonn nonlal covalent bonds and
N2k)+3HzB) ......................-2NH3
k) cise hydrides. All th ese
Fe, Mo shapes. Their bond
Electric discharye to PbH, as the size of
zH2@) + ozE) ---------------,--........- zHzo (s) the element increases from C to pb.
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11114
l,z[ii
\H-
RrIi:
\H-
R=[i:
-H--
AH: 210 6
254 6
Hrse
HrTe
23'l
270 8
HBr
HI
205.9
?31.5
sbI-I3
(siHa), etc'
@cH)o, (AlH3)6' (InH3)n, (GaH3),,,
evolve H2
These arc amorphous solids whicb dcaomP6e above 523 K to 8a-s'
LONE PAIRS
OccurrEnce. Water is essential to all forms
of life but distribution of water over the carth,s
surface Ls not uniform. Whereas deserts have oo
permaDent surface water, oceans cover vast areas c6-
(l .61 x 108 kmz), i.e.,78Vo oI the earth's surface.
Of the lotal-eslimated global supply of about
1.4 x 10e km3, the oceani and the lniand saline HH */\*
water bodies hold 97.3Vo and the fresh water
amounts to less thar.2.TVo.Most of the freshwater
oo
(2.5-2'9 x 107 km3) is locked up in Antartica ^ P=' too
and Artica glaciers. Fresh watcr lakes contain I
I .25 x 105 km3 of water, more than half of which
is in the.,tbur largest-lakes : Baikal (26000 km3),
Tirnganlka (2IlC0 km3), Nayassa ( 13000 km3; aod
/,\
HO-H
Superior (12000 km3). Other major sourceso[lresh
water are : ground water, springs and rivers. Tbc FI ga. Fha"a
fraction of fresh water readily available for human
use is only 0.0067" ofthe totalglobal water supply. ec.tre.
In nature, water is found is all the three (2.1) and hence the shared pairs of electrons in the
phases, r'.e. solid, liquid and gas.
11.9.1. Structurc of \f,hter Molecute and its
R
Aggregates
EE
In HrO molecule, the orygen is sp3-
AR
hence with fu-orbitals of hydrogen to firm polar molecule. Its actual dipole moment is l.g4 D
S
-overlap
(Fig. 11.6(c).
N
two.rp3-s, O
-H, o-bonds while the othJ, to,o con-
IA
Lain a lone-pair of electrons each. Since the oxgyen Hyrlrogeo bonding in water and ice. In the
IIT
atom is s23-hybridized, therefore, the geometfi of liquid state, tbe HzO molecules are held together by
HrO molecule should be tetrahedAl and the
ZHOH bond angle should be 109.-5.. But ex-
perimentally, it hasbeen determined that theactual
LHOH bond angle is 104.-5.. This maybe explained
follows :
a.s molecufes as shown in Fig. 11.7(a). Thus in the
In HrO, the oxgyen atom is surroundedbytwo liquid state, H2O exists as an associated liquid.
shared pairs, and two Ione pairs of clectrons. But
according to VSEPR (Valence Shell Electron pair
tn8-
Ice, the solid form of water. can exist in nine
O
-H bond has a bond len6h of 95.? pm.
In the crete
molecules HrO
molecule in asrn
Fis tl.idt. tures, it conde$es to cubic form. In the nornral
The elecrronegativity oforygen (3.5) is much hexagonal
,. . !9e,9ach or(ygen atom is terahetiraifi
trBtrer (uext only to fluorine) thaa thal ofhydrogen surounded by four other oxygen atoms,..s.. rhere
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11/16
VACANT SPACES
277 K.
,\ .t
H/
even during sevcre cold weather.
R
11.92. ProPerties of Water
EE
(a) Phlsical Pr
AR
properties of water
C
H-bonding between
physical constants o
S
N
lonisarion coDsrant [H+ j IoH-] (molz L-1 I 00tl x lO-la .9-5 x l0-l-5
Diclectric constant '7A.39 78.06
Viscosit)'at 293 K (rn centipoise) 0.8903 1.107
Electrical coDductivity (293 K/obm-l cm-l) 5.7 x 10-8
R
EE
aJ a universal solvent. Whereas solubiliN of ionic Electric current
AR
compounds takes place due to ion- dlpoie lntera- 2H2o(t) 2H2G) + o2@)
tions. (i-e. solvation of ions), ahe solubility of
C
urea, glucose, sugar etc. takes place due to the ter. Water is a weak electroll,te, i.e., it undergoes
IA
tendency of these molecules to form hydrogen ionizatiol to a small extent to givc HrO+ (aq) aoci
IIT
Eo= + 1 23Vl
S
->
IA
HrO molecules occupy the voids in thc crystal Ilardness ofwater is oI two types :
la!
C
tice.
(a) Tentpornry hardnesl and
S
I. For temporary hard water. The temporary 1. Lime-soda process. This method is
hardness of water is due to the presence of bicar- employed for
bonates of calcium and magnesium. It can be contains both t
removed by any one of the following methods : In this method,
W
1. By boiling. r is Ca(OH), and sodium carbonate are used. Where-
boiled, bicarbonates um as, slaked lime removes temporary hardness,
decompose to form ag- sodium carbonate removes permanent hardness.
nesium carbonates resPectivelY. Ca(HCO3)2 + Ca(oH)z-ZCaCot I +2H2o
A
Ca(HCOr), """'-"' CaCo3 I + CO2 + H2O CaCl2 + Na2CO3 CaCO: J + 2NaCl
(Tixnponryhadrrcss) Cal.carbonate MgSOa
----
+ Na2CO3 +MgCO3tr * Na2SO4
A
Mg(HCO3)2 """"".r MgCO: I + CO2 +H2O 2. Ion exchange method. Tbis is the most
(Tempotury ha n $) Mag. carbonatc modem method for softening ofhard water. In this
method, the Caz+ and Mg2+ions present in hard
These insoluble carbonates are removed by
water are exchanged by those present in complex
hltration and the water is rendered soft.
inorganic and organic compounds called ion ex-
2, By Clark's Process. This process is used on changers.lon exchangers are mainly of two types :
a commircial scale. In this process, calculated
(a) Inorganic ion exchangers - Fermutit
quantity The bicarbonates
methoil. Compelx inorganic salts like hydrated
presenti terreact withl.ime
sodium aluminium silicates, NarAlrSlO*. xHro
io form magnesium car-
bonates which can be easi.ly filtered off. have the interesting proPerty of exchanging Ca2+
CaO(s) +HrO ...........r Ca(OH), R
EE
Quick lime Slaked linre
AR
2CaCOrI + ZH..O
S
Mg(HCOr), + Ca(OH), .....- silica (Sior). The fused mass is washed with water
N
IA
(Repzratcd
Pa?nuttt) pemuttit)
anion exchang€ resins or timpl), anion exchangers.
MeZ + 2NaCl ...........+ NazZ + MgCl2
Let u-s nowexplain the working ofthese resins
(Exchausted (Regfierated
in demineralization of hard water.
pctmuut I ponutit) First ofall, hard water is passed though a tank
The soluble calcium and magnesiumsalts thus packed with cation exchange resins supported over
formed are rvashed away by water and the gravel (Fig. 10.13). All the cations present in hard
regenerated permutit can be used again. water will exchange with H+ ions furnished by
resins as shown below :
Advantages of th€ Permutit Process
(i) It is an efhcient process. 2 R-COO-H+ + CaCl,
resin)
(Cation exchar.ge (From hard water)
(i) This is a very cheap process since during
the process only sodium chloride is consumed -----------' (RCOO)2Ca + 2}{+ + ZCt-
which is quite cheap. (Exchoustcd rcsin)
)
DOWNLOAD FROM IITIANS CAREER
11122 Pradeep's
ovor gravel (Fig. 11.9). Here, the Cl- and SOo2- Similarly, the exchausted resin in the second
ions present in hard water exchange with OH- ions tank is rcgenerated by treatment with moderately
strong NaOH solution.
of the esins.
+
+
R-NH3OH- + Cl- R-NH3CI- + Na+ oH- ..........*
(E.rchausted rcsin)
(A ion ercharqc resin) An water) +
+
R-NH3CI- + oH- R-NH3oH- + Na+ + Cl-
(Exhoustcd tctin)
(Rcqenera4.t ftlitt)
+ Thus, the cation and anion cxchangers can be
zR-NHTOH- +
SO?- used over again and again. lt makes this proccss
(A io dchangercsii) (in wato) both efficient and cheap.
+ 3. Calgon process (reqttcsrrurion). In this
(R-NH3)2So?- + z(JH- process, Ca2 + and Mg3+ ions present in hard water
(Ethausted rcsit) are rendered ineffective (sequestrated) by treat-
Simultaneously, the Ht ioos coming from the ment $/ith sodium polymetaphosphate, (NaPOr),
hrst tank combine with OH- ions liberated in the where x is as high as 100, or more commonly with
sccond tank to form water. sodium hexametaphosphate. Nar[Na.(Pt\)61. Thc
Hr+ OH- + HrO trade name lor sodium hexametaphosphate is cal'
gon (which means calcium gone).
Thus, the water obtained by this method is
frce lrom all types of cations as well as anions. When calgon is added to hard water, the
Therefore, this method is particularly useful for R
Caz+ and Mg3r ions present in it combinc with
EE
obtaining drinking water from sea water and also sodium hoxametaphosphate to form soluble com-
plex of calcium and magnesium salts.
AR
ComPlcx salt(.roIublc)
ca(oocR), + 2H+ Cl-
IIT
(Dxhausted. resin)
2MgSOo + NarlNao(POr)61
(Fromhatdwalet) Sod.hexaoletaphosphale
zRcoo-H+ + Caz+ + 2Cl- NarIMgr(POr)o] + 2NarSOo
(Regenenrcd ru\in)
Complcx salt(rotuble)
HARD WATER
CATION ,/ANloN
EXCHANGE EXCHANGE
RESIN RESIN
GRAVEL
The complex calcium and magnesium ions do not form any precipitate with soap and hence reaclily
_
produce lather with soap solution.
ess can be used for laundry and household washing purposes
n is also used in rynthetic detergents to check the wistige of
rcmoing boiler scoles.
rEil r. Degre€ of hardtwis defined ar he mwber of parts of cokium catbonate or equivolant to voriour calcium and
magnesiwn sahs preseht in a nihon Frtt of wuer by mast. It ir eqressetl in ppn
ExtdMPLE. one liffe oI o ro,nple of hlnd baler conroin\ I mg of coct, aad t mg of Mgcl, Find oul the totol
hordness in terms of parts of CaCO , pr I d partt of troter by marr.
Solution. (i) Mol. ntass of Caclz = I 1l
Now, lllgof CaCl2 = lffigof CaCO:
.. I mg of CaCt2 = jf; x r mg of CaCO: = 0.9 mg of CaCO:
2. Estimntion of
IIT
The electrollic cell designed by Brown, Deg- gases evolved are burnt and returned to the cells in
get and Urey for the preparation of heary water is the second stage.
shown in Fig. 11.10. Fourth Stuge.'fhe tesidue from the third stage
is electrolysed again in order to increase its heavy
water content to about 99 per cent. The gases
evolved are burnt as usual and sent to cells in the
third stage.
Fifth Stage. ^fhe heavy water obtaincd as above
is contaminated with impurities of alkali and ordi-
oary water. It
is subjected to distillation and the
distillate Ls electrolysed when pure deuterium is
obtained. This is burnt separatelywith orygenwhen
100 per cent pure D2o is obtained.
ORDINARY
Calcium dcutcroxidc
heavy water, many compounds exchange Lheir ac-
IA
active metals like sodium and calcium react slowly with deuterium. Some of these exchange reactions
with heavy water to
form their respective are given below :
deuteroxides.
NqO + DrO -------' 2 NaOD
HCI + DzO + DCI + HOD
CaO + DrO ------.r Ca(OH)z NaOH + D2O i-- NaOD + HOD
4.Action with non-metalic oides. Non-metal- cHCl3 + DzO : CDCI3 + HOD
Iic oides such as phosphorus peotoxide (P2O5), Chloroform Deuterochloroform
sulphur troxide (SOr) etc. readily dissolve in heavy NHICI + D2O + NH3DCI.+ HOD
water forming their corresponding deuteroacids. NH3DCI + D2O +- + HODNH2D2CI
P2O5 + 3 D2O D3PO1 NH2D2CI + DzO i-' NHD3CI + HOD
-* Deutercpho+horic acid
NHD3CI + D2O i- ND4CI + HOD
SO3 + D2O -* D2SO4
Deutercsulphuric acid
9. Biological propefties. Heary water is in-
jurous to human beings, plants and animals since it
5. Action with metallic caftides. Heavy water
slows down the rates ofreactions occurring in them.
reacts with metallic carbides forming Thu-s heavy water does not support life sowell as
deuterohydrocarbons.
does ordinary water.
AloQ + lzDzo------.
Aluminium Carbide 11.113. Uses of Heayy Wat€r
4 A(oD)i * 1. As a moderator. Heary water is extensively
,.,,.SRi,n"n. used a.s a moderator in nuclear reactiorx since it
DOWNLOAD FROM IITIANS CAREER
Pradeep's i;i,t, lttii*i; qll
,vs down the fast moving neutrons a-nd thus helps deuterium. ThLs suggests that H3PO, has only one
:, rrnlrolling thc nuclear rcactions. ionizable H-atom ar.<lhence it is a ntonobqsic acid-
tracecompound. Heavy water is widely .
2. As a 3. For thc preparatlon of deuterium. Heavy
,ic<l rrs a tracer compound for studfng the hydrogen or deuterium is produced by the
rcihanism of many reactions, For example, when electrolysis of heavy water or by its decomposition
r,,n1-phosphorus acid (H,PO) is heated with by Na metal.
, o. only one H-atom is found to exchange with
ir, 2. I)eutcrium chloride may be preParcd by any oDe of the following methods :
peroxide can also be prepared hy thc action of At anode : 2NHoSOt ------+ (NH4)2S2Os + 2z -
phosphoric acid on barium peroxiclo : Amln. per6ulphate
3BaO2 + 2H3PO4 Ammoniuni persulphate formed around
anode is withdrawn and distilled with water to give
- Bur(POo), J + 3HzO2 Hzoz'
This method has thc advuntilgs over (NH1)2S2O' + ZH'O .----------+
BaO, -HrSOo mcthod sincs almost all thc hcary
netal (s.& Pb ctc.) impuritics prescnt iu BaO, and
2NH1HSO4 + H2O2
which catalyse the clecon.rposition oI H,O, are This process is now used only for the
laboratory preparation of D2O2, i.e. ;
removed as insoluble phosphates. As a rcsult, thc
resulting solution of H2O2 has good keeping IqS2O8 + 2 DrO-+ 2 KDSO4 + D2()2
properties. 2. By autoxidatlon of 2.ethylanthraqulnol.
11.12.2. Manufacture of Hydrogen Peroxide This is a new method and is widely used in U.S.A.
I. By electrolysis of 507o. HrSOa. Hydrogen In this process, air is bubbled through a lOVo solt-
peroxide is manufactured by the elcctrolysis o[ a tion of2-ethylanthraquinol in
benzene and
col<l 50'k solution of H2SO4 in an electrolyic cell cyclohexane when z-ethylanthraquinol is oxidised
to 2-ethylanthraquinone and HrO, is formed ac-
using platinum as anode and graphitu us cathode.
Thc reactions taking placc arc : R
cording to the following equation.
EE
2HrSOo 2H+ + 2HSO;
AR
C.H.
Atcotlutde'.2H+
- + 22- + Hzt o2
C
HlPd
N
Pcruxodisrlphuric
IA
acrd
IIT
(ii) Dehydratlon ln a vacuum desiccator.50Ta glycerine, acetanilide, phosphoric acid etc. must
solution of HrO2 as obtained above is taken in a
C
also be added.
S
dish and placed in a vacuum desiccator containing 11.12.4, Strength of Hydrogen Peroxide solu-
N
Sinriarly, 1ml of20 volume, i|volume and 100 . . 10 ml of C)2 at N.TP will be obtained from
volume HrO, solutions produce Z) ml, 30 ml and 6R
10sof Hro2
100 trll of oxygen at N.TR respectively. ffix
Let us now calculate the percentage stlength But 10 ml of 02 at N.T.P are produced from
of a 10 volume H.O, solution.
7 ml of l0 volume HrO, solution
Hydrogen peroxide decomposes on heating
Thus, 1 ml of 10 volume HrO, solution con-
according to the equation :
2HrOr"""+2HrO + 02 tuio. x 10gof HrO,
2 x 34 g 22.4li!Igs ar N,T.p.
ffi
or 24{D crn3 at N.T,p.
. 100 ml of l0 volume HrO, solution
. will
From the equation, .68 x 10 x I00
contarn
22.4 \tres of O, at N.TP are obtained from fffi i = 3.035c
2 x 34 or 68 g of tI2O2. Thts, a l|volume H,O, solution is approx. 37a
N t-.-FRQE_U..n\i,,9r9il* rrcsrnr,\u(;rH()r..
H.lI)t,t( )(;tr\ l,t,_tioXIDL SOLUTIONS
N,T,P =i=t'st
60;7
C
"--------- Oz
tion = 3.57 N
IA
Thus, the strength of Z) volume HrO, solution .. Strength of 1.6 N HrC), solution
cl
= @.7 =l.6xL7C
_ Step 2, To cakulak the equivalent wciglt ol Now 68 g of HrO, gives 22,100 ml O, at N.Tp
H,O,
.'. 1.6 x 17 g of H2O, will give
Consider the chernical equation,
2241n
2H2Oz '-----'- ZH2O * Oz
68 x 1.6 x 17 =8960 ml of O, at N.T.p
6E parrs by Eight 32 porir b, srighr
From the above equation, But 1.6 x 17 gof HrO, are pre sent in 1000 ml
32 parts by wt. of oxygeE rre obtained from 6g of HrO, solution.
parts by wt. of IIrO. Hence 1000 ml of HrO, solution gives 8960 ml
.. 8 parts by wt. of orygen will be of 02 at N'TP
obtained
from
.. 1 ml of HrO, solution will give = 99
1000
lTpartsbywt. of HrO,
#rt= =8 96 ml of Oz at N.Tp
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1 1/30
Pradeep's
Hence the volume strength of 1'6 N H2O2 Step 2. Tb culculste the volwne of Ozliberated
Irf{Nl PLIt 1 1.-3. Calculate the volume strength 1 titre of 2M HrO, solution contaios H2O2
of s 3Eo solution of HzO2. = 689
SteP 1. Io cdlculate the omount of . . l(X) cm3 of 2M HrO2 solution will contain
HrOrpresent in one litre ol 3o/o soltuion. Hzoz
100 mt of HrO, solution contain HzO2
=**"100=6.88
1000
=3c
. . 1000 ml of HrO, solution will contairr The cquation rcpresenting thc decomposition
? of HrO, is
HrOr=ffix1000=309 zH.Oz ZH|O * Oz
Step 2. To calculate the volume strength 2 x = 3.1 6ti g 22400 cml ar STP
-
Consider the chemical equation, Now 68 g of HrO, at STP give O,
2I{2o, / llr1l I 02 : 22400 cml
2xy=6Ag-"+ 22 4litrc. at N.T.P.
. . 6.8 g of HrO, at STP will evolve O,
Now 68 g of HrO, give 02 at N.TP
z24oo
= 22'4litues - x 6.8 -- 2z4o cm3
6u
. . 30 g of HrO2 will give 02 at N.TP = Z24litres
21.4
,30 :
R
EXAMPLE 11'5' 30 ml o[ a H rO rsolution ofter
EE
= 9'88 titres
68 acidifcatnn required 30 ml ol NII0 KMnO4solution
AR
= 9880 ml.
Iot conlplctc o.\idation- Colculate tlu percentage a,td
C
:34x2=68C = ll lflo.
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HYDROGEN
Step 3. 1"o detcmtine tl& volunrc strcngth oI But 1.7 g of HrO, are present in t00() rri
HzO2;ohttion. HrO, solution.
Consider the chemical equation, Hence Lff)0 ml of HrO, solution give :. -ir,it
2 H2O, -"+ lltr1l I O, of O, at N.TP
689 22400 nl a! N.T.P
-r -'j
Problems oD perccntage strength, norDality, molariry and volume srrengrh of Hro, canE easily sotrL .t 1..
the applicalion of the following relations.
R
EE
r'
AR
'
FOR.,P,RAC,. I.CE
C
"RO7LEM7
S
1. Hydrogen peroxide is more deose (L.rl4 Melting poiDt 2',12.4 Density (Lquid
g/cmr) and more viscous than water. This is due to (K) ar 298 K)
the reason that the molecules of HrO, are even (8 cnr ')
more highly associated through H-bonds than Boiling poiDt 42i Viscosity at
HrO molecules. (cxtrapolared) 294 K
(K) (Centipoire)
1.9 Dielectric con-
Pr9SSUre at stant of 298 K ,
H2O
situtr iodide solutiott
Sod lrydroperoxide
HzOz .-_....rH2O + [OI
2NaOH + H2O-r"--'+ NarO2 + z}1zo
Sod peroxidc 2KI+H2SO4 +[O] K2SO4 + 12 + H2O
Ba(OH), + H2O2 ----------+ BaO, * 2HrO -
3. Oxidising and reducing character. 2KI + H2SO4 *H1(), "-""+ K,SO1 +1, +2H2o
Hydrogcn peroxide bshaves as an oxidising as well or 2I- + H.rO2 + 2H+ -------.Iz + 2H2O
as a reducing agent in both acidic and alkaline
solutions. Thc oxidation state of oxygen in (iv) Hydrogen peroxitle oxidi.tes icc-cold
hydrogen peroide is - 1. It can be oxidised to O, o cidif ed potas s ium di c ltorno t e s o h li ot t ( c ont q ini try
r
H2S + H2O2 """"-- 2 H2O + S always produced by the combination of HzO2 with
the orygen atom released by the strong oxidising
C
:
HrSOo (aq) + H2O o +
N
or 2MnOf, + 6H+ + 5Hr0, ----"'' (ii) It ruduces fenic salts to lenous solts in
olkaline medim't
zMrf+ + 8H2o+502
2Fe3+ (aq) + HrO, (ar) + 2 OH- (aq)
(ii) It reduces acidified potassium dichromate -
2Fe2+ (aq) + ozG) + 2H2O (t)
solution. As a result of this reaction, the orange
colour of KrCrrO, changes to green due to the |ormu' (iii) It reducer alkaline potassium fenicyanide
tiotl ol chrotnium salt. to p ot o s sium feno cyanide
IlCrrO7 + 4 H2SOa .-...._ 2 Kr[Fe(CN)r] + 2 KOH -----""'+
IqSO4 + +4HrO+3[0]
Crr(SOo), + H2O + [o]
2 Kr[Fe(CN)u]
11.12.6. Uscs of Hydrogen Peroxide (rr) It is used io the laboratory for detecting
(i) The most important irdustrial use of the presencr of ckomiun, titaoium and vanadium
HrC), is as a bleaching agent for delicate materials salts with which it yields peroxides of characteristic
colours.
like textiles (silk, wool), paper pulp, straw, leather,
(x) 93Vo HrO, so\ttion is used as an oxidant
ivory, oils and fats.
(r'i) Domestically, it is used as a hair bleach for rocket fuel and as a propellant for torpedoes
and submarines.
and as a mild disinfectant.
(xr) It is used as antichlor (to remove Clr) in
(rr) It is extensively used to manufacture iaor-
ganic chemicals like sodium perborate andpercar-
texti-le industry to remove cxcess of chlorine after
bleaching operations.
bonate which are important constituents of good
quality detergeDts. U.12.7. Tbsts of Hydrogen hroxldc
(iv) It is used in the production of epoxides, (i) H2Oz on treatnent with atr acidifed solu-
proplyene oxide and polyurethanes. tion of titanium salt gives a yellow or organc colour
(v) HrO, is also used in the synthesis of hydro- due to the formation of pertitanic acid (H2TiO4)
quinone, pharmaceuticals like cephalosoporin and Ti(SO4)2 + H2O2 + 2 HzO ------ HzTiOl
food producs like tartaric acid. + 2 H2SO1
(vi) HrO, is increasiagly being used in en- (li) It liberates iodine from KI solutionwhich,
vironmental cheElstry to control pollution by in turn, gives blue colour with starch solution,
(i) treatment of domestic and industrial effluents (r'ii) When an ethereal solution of HrO, is
(ii) oxidation of cyanides and restoration ofaerobic shaken with acidified solution of IQCrrOr, blue
ca[ditioD.s to sewage wastes.
(ur) It antiseptic under the name
R
colour appears in the ethereal layer due to the
EE
is used as an
formation of chromium pentoxide (CrOr)
perhydrol for washing wounds, teeth and ears.
(iv) When brought ir contact with H2O2 solu-
AR
of HrS present in the air oo lead paints. (v) It decolourizes acidified KMnOo solution.
S
N
IA
IIT
1 Peroxides. Melallic 6ides which on reatment with dihue acid|; prod,uce hydrogen peroide are called peroider.
For fiample, NEO2and Ba02. lD lhese peroxides, the two oxygen atoms are linked hy a single bond and each
oxygen atom has aD oxidation state of-1. In other words, all peroxides crl)tain a peroxide ion ( O3-) haviDg
the structure -: O-O :-. In lhis structure, all the electrons are paired and hence all peroxides are diam{rP.
netic
'fhere are certaiD other oxides like PbO2 and MD02 which may be mistaken as peroxides. These con'tpouDds,
however, do not Sive H2O2 on treatment wilh dilute acids. As such these contpounds do Dot clDtain a peroride
ion (o1-) and hence they cannot be called as peroxides. Actually in these compouDds the rwo oxygen aroms
are linked to the metal atom by a double bond and henc€ are called dioxides, i.e., O = Pb = O (lead dioxide)
and O = Mo = O (mangenses dioxide). In dioxides, rhe oxidation state ofeach oxygen atont is -2.
: Superoxides, Bcsides peroxides, alkah metals also form higher oxides callcd supcroxides. For example,
Potassium superoxide (Ko2), rubidium supcroxide (Rbo2), c.esium supero(ide (csoz) etc. All rhese supcr-
apPlTp:v@lr&KNowuEe6-E{C-ONilip.
lil 3 o the tbllowing types :
mber of tbe elemcnt (M) can be deduced fronl the
orygeo as-2 aro callcd normaloxides For cxaDrPle,
HzO, NazO, MgO Al2O3, CO2 etc. All these oxides contairr M-O bonds'
number ortbe
(iD poly;xues. .Ihese oxides colrtai|r morc oxygen than \pould be expecred from thc oxidation
ilcmeni ltrl;. mese trave becn further classifierl into Peroxides, aDd superoxides'
ll.l23.Structur€ofHydrogenhroxirle.Thereareseveraladvantagesofhydrogen
tionof H2.TW
are : electrolysis of water and
C
90 2"
cost of proiuction of H, bY
IIT
H
----:i----l:---
\
i01.5. electrolysis of H2O is so high
that almost all H, is obtained
from natural gas which itself is
o o in short supplY. The other
method involves series of ther-
mochemical reactions in which
the only things consumed are
water and heat and the onlY
nroducts are hvdrogcn and orygcn while all other
,pccies are recycled. Clne such thermochemical
The coal and oetroleum reserves ofthe world
reaction cycle is
arc limited and ari fast dwindling. Therefore, the 175 K
3 FcCl2+4 H2O-Fe3O4 +6HCl + Hzll< Z
475 K
2 Fcaoa + 12 HCI + 3 Cl2
6FeClr+6H2O+Oz
-
7L5 K
2 FeCl, .-..._ zFsclz+Clzl x3
2112() zHz+ Oz
economy. -
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HYDROGEN 11137
Whether any of the methods listed above can fuel cells are rountinely used as power source on
produce H2 cheaply enough to make its use prac- spacecraft. A 4 5 megawatt fuel cell power plant
ticable is a most distant possibili(y. The other prob- (with conversion efficiency of 70-85%) has been
lem is to hnd out an effective means of stroring established in Tokyo. Unfortunately such fuel cells
Hr. The gaseous H2, because of its bulk, is difficult are too expensive to be used in consumer oriented
applications in developing countries like India.
to store, but liquid H2 can be stored relatively easily
The combination of all these potential uses of
and safely in cryogenic tanks (already in use for
hydrogen could bring a fundamental change in our
space programme in U.S.A.). It is also feasible to
way of life, giving rise to what is called hydrogen
transport liquid H, by road or rail tankers of20,000
economy.
US gallons capacity. It can also be stored in under-
ground tanks and transported by pipelines. How- 11 .'14. Use of Liquid Hydrogen as a Fuel ::l:, :i: I
,
ii i ,:i r i::i
ever, it may not be convenient to store liquid H, in Use of hydrogen as an automobile fuel has
a home or a car since the boiling point of H, is very many advantages :
low (20.4 K) In either case (gaseous orliquid form) (i) First the heat of combustion of H2 is by far
H, must be kept out of contact with o4gen or air the largest, i.e., 115 megajoules per kilogram
with which it forms explosive mixtures. The only (MJ/kg) as against 43 MJ/kg for a typical unleaded
alternative left is to store H, in a metal or in an alloy gasoline, 39 MJ/kg for ethanol and Z) MJ/kg for
(such as iron-titanium alloy, LaNir, Mg-MgHr, methanol. Thus, an automobile engine is ?5 - 50Vo
more efficient when it uses H2 rather than gasoline.
Ti-TiH, etc.) as interstitial hydride.
The gas can then be released on mild heatinq.
(i) The exhaust is free from pollutants like
CO, CO2, Nq, SO2, hydrocarbons, aldehydes and
R
ln an automobile, for example, this storage system
EE
would replace the gasoline tank. The heat required lead compounds.
to release H, from the metal hydride could come
AR
Ifthe problems discussed above can be solved, (iv) Internal combustion engine can be easily
S
not only can H, be used to substitute gasoline as a modihed for use of hydrogen as fuel.
N
IA
fuel for transportation, but it could also replace The most cffective means ofstoring hydrogcn
IIT
natural gas for space heating. Moreover, because is in the liquid form. The liquid H, is widely used
H, is a good reducing agent, it could replace carbon as a rocket fuel since it gives higher thursts than
(as coal or coke) in many metallurgical processes. most of the other frrels.
And, ofcourse, itwouldbe abundantly available for The range of supersonic aircraft could be in-
reaction with N, to produce NH, for fertilizer creased if the aircraft used liquid H, as a fuel.
manufacture and other use'. Hydrogen can also be Further hlpersonic aircrafts would also become
used as a direct substitute for electricity which can pqssible if liquid H, is used as a fuel.
be generated by wide spread use of fi.rel cells. The
c'?*ne,entaa,|*Aue.-q*i,p,ns.,
t.r I lVhich isotope o[hydrogen is used as a tracer in orpxnic renctions.
Ans. H)'drogen has three isotopes, qz. H, D and T Due to dittereDce in masses, the rate constants ofthqse isolopes
with the saore substratc are differeDl. ln orher worcls, both D andT shw irotope effecl But since T is not only
raclioactive but is also least ahundant hydrogeD isotope, therefore, D is used as a tracer to study the mechanism
oforganic reactions.
1.; I Name one examPle of a reaction in which dihydropen xcts (i) rls nn oxidising agent nnd (il) os a reduclng
agent.
Ans. (i) In rhe reaction ofdihydrogen with merals ro forD] n.tcral hydrides, it acts as an oxidisiDg agent.
Heat
Na 1s1 + Hz@) :::- 2 Na+H- 1.r; ;
;
23K
C
Hz@) G; G)
N
sunlight
IA
Ans. Conc. H2SO4 on absorbing HrO from moist I{, produces so much heat that hydrogen catches fire.
Q. 5. Why is diorygen paramagnetic ?
Ans. M.O. diagranr shows that O, has two unpaired elecfirtny and thus shows paramagnetism.
Q. (r. Can marine species live in distilled wnter ?
Ans. No, because distilled HrO does not contain dissolvecl Or.
Q. 7. A sample of hard water is allowed to pass through an anion exchanger, WII it produce lather will soap
eaSily ?
*t' and Mg2+ ions are still prese nt and these will react with soap to form curdy white ppt. Therefore,
Io.._9'+
it will
not produce lather with soap easily.
Q. tt. Can dlstilled water he called as deionised water ?
Ans. Yes. Distilled water does not contain any cations and anions and hence can be called as deionized water.
Q. 9. Explain why oxide ion is called a hard ion ?
Ans' Oxide ion is very small in size and thus cannot be easity polarized and hence it is called a hard ion.
{). I{1. Anhydrous BaO, is not used for preparing HrOr. \ilhy ?
Ans. Anhydrous BaO, is not used because the BaSO4 formed during the reaction forms a protective layer around
unreacted BaO, and the reaction stops after sonte tlnte.
fr
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HYDBOGEN 1 1/39
Q. l. Which isotopc of hydrogen (i) does not contflin neutrons, (ii) contslns equol number of pmtons end
Deutrons, (ii) is radioactive.
Ahs. (i) proliunr Gl) deuterium (iii) tritiuD.
- Q. 2. Why is dlhydrog.n Dot prefered in hatloons these days ?
Ahs. Dihydrogen is highly combustible and hence rs likely to cstch fire in presence of exce$s ofair
Q. 3. Name one compound each in which hydrogen exists in (i) +I and (ii) -1 oxidation stote.
ADs. (i) HClor H2O or NH3 ( )NaHorCaH
Q, 4. What is the importahce ofheflr] wat.r ]yith reg.rd to nuclear power generation ?
Ans. It is used as a moderator to slow down the neutrons produced as a result of fission and thus belps to coDtrol
the nuclear reactioos.
Q. 5. How is heaq vater produced from ordinary wnter ?
Ans, lr is obtained by repeated elecrrolysis of ordlnary warer contaiDing 3% NaOH.
Q. 6. WhAt do you mean by 15 yolume HzO2 solution ?
' Ans. 1cm3 ofa 15 volume HzOz solutioo gives 15 n)lofOz ar NTP.
Q. 7. Namc two compounds which rettrrd the decomposition ofH2O2 solution.
Ans, Ac€tanilide, glycerol.
Q. E. Colculste the smount ofH2O2 present in l0 ml of25 yolume H2O2 solution.
R
EE
Ans. 10 ml of 25 volunre H2O2 liberate O2 = to x 25 = 250 nrl at NTP
AR
.
S
Q.9. Hydrogen peroxide is used to restore the colour ofold oilpaiIltings contoining leod oxlde. Write a balarced
IIT
- 22400.,\ 0 et
''. 0 91gof H2O2will produce 02 =300nrlatNTP
. volume strength = 199 = ro
ar
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11140 Neul Coutse Clrent i strq
Ans, Deuleroace9ene is formed, (hq + 2D2O Ca(OD)z t DC = CD
-
Q. 15. Whnt is deminerolized wnter ? IIow is it obt.nillcd ?
Ans. Water which docs not contirio cations and anions is called den'rineralized waler. 11 is obtained by PassiDg
ordinary water through ion exchange reslns.
Q. 16. The hoil ing point of H2O is higher thfln that of fI2S. ExPlain.
Ans. Due to extensive iDternlolccLr lirr i I -bondiDS irl I l2 o, I hc b.p, of H2c) is ntuch hiSher thaD that of H2s.
Ans. Due to lower dielectric constant of D2O over I'12O, NaCl is less soluble in DzO thao iD H2O'
Q, 23. Explain why heryllium forms a covalent hydride while calcium forms sll ionic hydride' R
EE
Ars. Because of higher electronegativity (E N = I 5), Be forms covirlent hydride while due to lower
AR
Ans. Due to lower bond dissociarion ene rgy of protium bonds in H-o-I{
thaD dsuterium bonds iD D-o-D,
IIT
Ans. Hydrogenation means addition otH2 in Presence ofa catalyst to multiPle bonds to tbrm saturated compounds.
\ior Pr orPd
For example, CH, = gg, + Hz ........-..-................. CH3 - CH3
Ethene 473 K Ethane
to say thot hydrogen can l)chave rs a metal ? stlte the conditions under which such hehaviour
Q, 2t, Is it correct
can bc possible ? \:( / li /
Ans. Yes, H2 can act as a metalunder very vcry high pressures'
Q.29.Ionichydridesorcfrequentlyusedtolemovetrlrcesof\YnterfromorgllniccomPouhds.whatisrtnderlyin8 /
hrsls oithis process ? \1(''Ir- I /l '
is a strong Bronsted base and hencc reacts $'ith I 12O readily liberatin8
H- H2 gas
Ans,
\
al
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HYDROGEN 11141
Ans. lDteractlon ofH+ and OH- ioos of H2o wth the inrioD and the carion ofa sall respeclively to give the original
acid ard the origiDal base is called hydrolysis. For exan]ple
Na2COl+2HrO _2NaOH + HrCO,
sart Basc Acid
r: . Hydrslion, olthe other hand, nleans addition of H2O lo rons or molecules to form hydrated ioDs or hydratcd
salts, For example,
Na+cl- + Hro * Na+ (oq) + ct- (oq)
Sslt
CUSOa+5H2O- CUSOa . 5 H2O
<Colourle$) (BIuc)
1 Explain w-hy hydrogen is besi plac€d separatety in thc periodic rable ofelemcnts.
(N.C.E,R.T)
S
S!c. lll 4. i
flow is dihydrogen prepared (i) from warer by using reducing agen! (id) in rhe laboraiory in pure
N
W.b.E.t.f)
5. wbat is meant by \mter gas shifr reactio''? Describe its use for the preparation ofdrhydrogcn.
IIT
(N.c.B.R.T.)
Describe the industrial applicaiions of hydrogeD depndcnt oo :
(i) the heat liberated when the aloms arE made to combinc on thJ iurfacr of a metal.
(ri) its effect on unsaturated organic slstcms in presence ofa cataly*t.
.
(ir'i) its abiliry ro combine wirh nitrogen uoder specific cooditioDs (N.C.E.n.T)
1. Explain the correct context in which the lbllo\ving terms are uscd.
(i) diprotium (r'i) dihydro8en (i!i) protoo aDd (iy) hydron.
N.C.E-L-T/
t. Name rhe i'otopes ofhydrogen. What is the imponancc of the heavicr isotopcs of
hydrogen ?
(N.c.E.R.r)
9.How will you prepare healy hydrogen is lhe laboratory ?
10. How many allotropes ofdihydrogeo are known ? What is their importance
? (N.C.E.R.T)
11. Cornplete the following reactio,rs :
(i) Cuo (r) + H2 G)..* (i,) co G) + H2@)+ (N.CE.R.T)
icc.l !.3. 12. How is dihydrogen obtarned from
to 11.1. (i) water (r'i) dilute acids (ir]) atkalies ?
13. How does dihydrogen react with
(i) Blue litnrus soturion (ri) chtorine (ai) flourine (iv) nitrogen (y) sutphur (yi) (arbor
(vii) sodium (vxr) ferric-ferro oxide (mag[etic odde) (E) carbon mooGide ?
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11142
Pradeep's
(N'C'E'RT)
31. why is ice less deNe than water aDd what kind ofattractive fotces must be overcome to olelt ice ?
C
(N.C.E.R.T)
S
N
(r) CJo (r) + H2o (f .... (,,) Na2o (r) + H2o (D- (iii) Fe ('') + Hzo (s)' (N.C.E.RT.)
IIT
33.
- Elcmeots witb atomic numb€rs 17 and 20 form comPounds with hydrogen Write the formulae!f
ttr"r" rompounOs aDd coolpare their chemical behaviour in water'
q'C'E'R'T')
35. Discuss the Principle and method of sotlening of hard watcr by organic ion cxchaDge resins'
(N.C.E.R.T)
(6) Sodium peroxide is lreated with cold dilute sulphuric acid and the r€sulting mixturc is cmled below
n3K
C
61' Ho', is a sorution of H202 concer)rrated ? why cannot ir be conc€Dtrated by disiirario[ a[ ordinary
Pressure ?
62. Justify the statemeDt ,An aqueous solution of h,drogeo percfiide
is weakly acidic,,.
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11144
Pradeey's tli;Nii4
63. In the preparation of hyclrogen peroxicle, the use of PhosPhoric acid has atl aclvantage over dilute
sulphuric acid. ExPIain.
64. Name the conrpound of hydrogen ancl orygen which acts both as an oxidising as well as a rcducing
agent. Give one n:ethod for its preparation.
65. How does HrO, act as a bleaching agent ?
How is dihydrogen prepared oD a commercial scale ? Give one convenient method for
preparing
4.
S
Give equations to show the reactions of dihydrogen with : Na, Ca, CO, N, S' Cl and CuO.
IA
5.
What aie hydrides ? Discuss their various types. Ho$'are they formed ?
IIT
Scc" i l.tt, 6.
7. Discuss briefly the nt types of hYdrides'
what doyou mean diffeient methods used for softening of hard water ?
S cc. 1 i.9. E.
to ll.l2. Briefly otplain the
the structure of (a) water in the gaseous and liquid states (D) ice. Explain why water
exPands
9. Discuss
on freezing ?
is the process
Give the equation for the auto-oxidation of 2-ethylanthraquinol to produce HrOr. Why
I ().
called auto-oxidation ? What is the advantage of this prooess ? Give one example of a reaction
with
stronger
equation in which ozone acts as an oxidant but no oxySen is produceQ. Which element is a
o*iOant than ozone ? (West BmgalJ.E,E' 2001)
11. Horry is hydrogen peroride prepared in the laboratory and on a commercial scale ? Giving four
6f .udn gie
iiactions starement that hydrogen peroxide acts both as an o:<idising as well
lustiryifre
as a reducing agent.
t2. Write notes on:
to II.l4 (a) Hydrogen economy and (D) Liquid hydrogen as a tuel of the future'
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ADDrriuNAtu_QEr-u-L-!Nr-qBUAf!9|!'--':":',
Oz, Ag and Hg at tow temperatures to tbrrn their respective
hydrides'
It combines with
Or+2H-HzOz ; Ag*g.--AgH
nract wilh the substance to be reduced Ls called nascenl
3.ComparisonhetweenAtomicandNascenthytlrogen.Mainpointsofdifferenceare:
atomic hydrogen is produced at
C
elevated temPeratures.
N
(ii)Nascenthydrogencanneverbeisolateclbutatomichydrogencanbeisolated.
IA
(iii)Reducingpowerofaton:ichydrogenismuchgreaterthanthatofnascenthydrogen.
IIT
Ingeneral,thereactivityofthethreeformsofhydrogenincreasesintheorder:
Molecutw lrydrogen (H2) < Narcen! hydrogen < Atomic lrydrogen
temperatures to
4. ained by subjecting a stream of molecular hydrogen at o-rdinary
in natu.re (half life = 0'33 sec) and conrbines
silcnt el 30,fi)0 volts' It is'very reactive
directlywithPbandStbrmingtheirrespectivehydrides. a little of HrSoo or
of heavy water containlng
5. Heavy hydrogen. It is manufactured by the electrolysis
NaOH to make it a good conductor of electricity'
.P, SPECTAL
!1. SuD.llta'11l'li QUES7'10NS (Lot motwith LI.'t:)
Here, Cf + gets midircd to Cr6+.
Q. l. The proceds 12 H2@) + c- H- (B) ls en- ReduciDg lgent I
dotherElc (AII = + t5l kJ Eol-l),
- yetsalr like 2 K3lFe(cN)61 + 2 KoH + Hzo2 ..*
hydrides are krowD. Hop do you accourt for
this? 2& [FC(CN)5] + 2H2O + c}2
An& It is true thar formarioD ofhydride (H-) ioD is an Herc Fe3+ gets reduced to Fe2+.
endothermic process, yet alkaliand alkaline earth
mctals form salt like hydrides. This is due to the e. 5. A rvhite solld Is elthcr Nr2O or Ns2Or. A plect
reason lhat high latdcr enersr released (eDerry of red lituus pspcr tunr6 rvhite wheo it is dlpped
releas€d duri[g tbe formatioo of solid meGl into I fr€shly mode aqueous solution ol the
hy whit solid.
M (i) Identtly ahe substoncr ond explsln wltlr
DC balanced cqustion
gas. (ir) ExplaiD rhatrould hrppeD to thc rcd titErs
Statues costed withwhitelead or long.xpo6ure if thc whitc solid ver€ thc other coDpoutrd.
Q.2.
to atmosphere turr black altd the origiDal (LI.T 1999)
colour con be restored on treatDentwith H2O2. tu& (r) NEO2 + 2H2O 2NaOH + H2O2
whv ? (Roo*ee 1987) -
H2Oz thus produced turns rcd litmus paperwhite
Ahs. On long exposure to atntosphere, $hite lead is
converted into black pbs due ro the adion of R due to its bleaching astion.
EE
HzS present in the atmosphere. As a result, 0i) Na2O + H2O 2NaOH
-
AR
statues turn black. NaOH thus produc€d will tum red litmus blue.
_*
C
PbO2 + 2ll2s PbS + 2H2O e. 6. Atr eleDent h86 its tDarlEum sDd EiDimum
+ n s\il -m respccdvely
S
H2O2, the black pbs gets oxidised ro white the possibllity of uDdeBo_
IA
,n?
PbS + 4 H2Oz .+ PbSOr +,1 IIzO (We€ Benrat t.E-E. ZN3)
(.r A mixture of hydrazine and IlrO2 \yith Cu (II) Ars. Hydrogeo hasm imumaod miDimumqidation
-r states as + I and 1 respcrtively. Eement! of
catalyst is used as r rocket propellarlt. \yhy ? -
goup 14, ie., C, Si, Oc, Sn & pb caD also have
ADs. 'Ihe reactioD between hydrazine and H2O2 ts m$dmum and mioimum qidaaiotr slates of + 4
btghly exothermic and is acrompaned by a larte aDd -4 rEspcctilrly. But all these elements u Dder_
tncrease ln lhe volunle olthe productsand hencc go disproportionation reactions in some of their
thts ntl{ture is Lised ari a rocket propllant. compounds. For eEmple,
o
.NH2-NH2 (/)
Cu (ll)
il
- 2 H20, 111......._ 2H---C-H + NaOH *
N2G)t+4H2oG),l (o.N.ofC=0)
,.1 I Ilydrogen peroxide octs both as an oxidising CH3OH + HCOONa
agent ilDd as a reducing agent in alkaline solu_ - 2) (oN'ofC= + 2)
(O.Norc =
tion towards cerlsin lirst rorv traDsition metsl Therefore, the value ofn is l.
ions, llllEtrnte both these properties ofH2O2
Q. 7. (8) Is it pGible to rlEove complcrely by hoilhS
using chemicnl equotiolls. (l.I.T. 1998) the temporary hsrd[ess due ao Mg(HCOr2 ? -
ADs, Oxidising ag.[t: (b) Cstculrte thG molarity strergth of II2O2
2Cr(OH)l + 4 NaOH + 3 H2Oz..--- solutlor mrrLed j30 volumd.
2NazCrOa+8H2O (tyed Bengat t.E.E. 2004)
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11148
,ATSJ SPECTAL
C
S
N
Q L A5 0 cm! solutlon ofH2or lib'rates 0 50tgof .. I 0 r.,m3 of I{2Oz solution will give
IA
From the above equatioD, tIzO2 = 12 solution of potassium iodiile rvas added 'Ihe
ioiline liberated required 20 ml of0 3 N sodium
34 g of HrO, e 254 g of I, thiosulphate solutioD' Colculote the volume
., 0 508 of 12 willbe liberated from strength of H2O2 solution. (l.I.T 1997)
B
Ans. Step L To (letemine the notmality of Hror:tolu-
Hror=i*x0 s08=o 068 I lrcn.
(6) The deomPcition of H2O2 oc{urs as Let the normality of the H2O2 solution be Nl
2H7O2 2H2O + Oz Acrording !o tho question,
25 nrl of Nr Hzoz = 20 nl of 0 3 N Na2s2o3 solution
2x34-68I 22100 cm3 at NT?
.. 0.068 of H2Oz uPoo decomPositionwill Sivc
or 25xNl =20x0 3
o,=ffxo068=224 I or N,=20iro3=uzlrn
Thut, tlrc normaLity ol the given Hzoztolulion
(c) Now 5 0 cm3 of H2O2 solution gives
=0 24N
Oz = 22 4 cm3 at NT?
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HYDROGEN
11149
Step 2. To detetmine the omount of I!2O2in 25 ml
2MoO;+5HrOr+6H+...-
.tolution
1000 nrl of I N H2O2 solutioo contain H2O2 2Mnz++502+8H2o
=178 (i, Itr neutral medium,MnOf, cxidiset MnI+ to
. 25 ml of 0 2,1 N H2O2 solutioo willcontain MnOr.
9o1- z+ze-
= 33.6 nrl at N.TP
Now, 25 ml of H2O2 solurion give
-2c
MnOr+CrOo2-+4H+ *
02 = 33 6 ml at N.TP
. Mn2+ +2COr+2HrO
1 ml of H2O2 solution will give 02
R
EE
336 or 5MnO2 *5qq- +20H+
=-i-= t.sqt -
AR
lo\rs that
,
N
acidilied with dilute H2SOa. The same volume Saep 'fo determine the numbet
-2. of nales oJ.
ofKMnO{ sohrtioh isjust decolourised by l0 ml CrOf,- present in 10 tnl oJ 0.2 M lotlitm oxalate.
of MnSOo in neutrnl medium simultaneously No. of nloles ofsodium oxalate
forming a dork hrown precipitate of hydrated
= Molarity x volume tn litres
Mn02, The browh precipitat; is dissolvcd in t0
ml of 0.2 M sodiuh oxalate uhder boiling con. =o zrffi =2 xlo-3mote
dition in the presence ofdilute HrSOa, Write the
Step 3. To calculale the molatity of HzOz
balflnced equations involved in the reactions
and calcnlate the Inolflrity ofll2Oz. From Eq. (iy), it fo ows rhat 5 qO?- = 5 H2O2
(I.I.T. 2001) or 2 x 10-3 mole of CrOo2- 2 x l0-3 mole
Ans. Stcp =
1. To rrite balonced equatioru for tlrc reac- ofH202
Itons inyolved.
(r) In acidic medium Now2 x l0-3moleof H2Oz is present iD 10 ml
, MnO; oxidises Hzozto 02.
ofH2O2
=0.2M
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1 1/s0
Ned CouYse Chentisttg
UfrT"LE ;UE9TI,ON9
(a) CaCO, (6) Ca(OH),
l. whiob of the followll]g statemenL\ is nlost ap-
plicable to hydrogen 'l It cao act (c) Caclz (d) Hcl.
(c) as a reducing agent
In the calgon process of softeniDg ofwater, \r'hich
(D) as an oxidsing agent of the following is used 'l
(c) both as oxidisirg aDd reducrng agents (.r) Sodium polymetaPhosPhate
(d) Deither as ao oxidising Dor as a reducing agent' (b) Hydrated sodium aluminium silicate
Hydrogen contbiDes with other clements by (c) Cation exchaDge resins
(a) losin8 an electroo (d) Anion exohaoge resins.
(b) gaining an electroD 10. Hydrogen will Dot reduce
(c) sharing an electron (d) heated cupic oxide (b) heatcd ferric oxide
(d) l6inB, gaining aod sharing ofan electroo' (c) heated slannic oxide
l. Ttrs tirst ionization ener$/ (kJ mol-l) for H, Li, E (d) beated alunrinium oxide.
Na has one of ihe followirgvalues: 1681' 520, 1312,
I t. Thc oxidation states exhibited by hydrogen in its
495. Which of these values mrresPonds to that of
various c!n]pounds are
hydrogen ?
(4) -l only (6) zero only
(a) 1681 (b) t3tz
-l zero (d) +
R
(c) + 1, and 1 oDlY
(c) 52o (d) 4es.
EE
4. The correct increasing order of the acidity of CO2'
The oxidation stirtes of the most electrooe8ative
AR
I{2O and H2O2 is element in the products of the reaction, Ba02 with
C
(c) HzO < HzOz > COz (c) and (d) ard + l.
-2 -2
IIT
wL-:r<s 9,a
l.c 2.d 3.b 6.b 7.b E.' 10. d
11. c tz. b 13. c
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'I 1/5'1
HYDROGEN
(./)ooe nrole of sulphuric acid, one n]ole of (b)H-(@t) + tl2O(D oH-(.,rJ) + rl2G)
peroxomoDosulphurlc acid and one mole of -
hydrogen Peroxide- lt l "' (c) H- + H2O -..- No reactior'l
Which cootains both polar and non-polar bonds ? R
(d) None ofthese. "; :.:
EE
(a) NHaCI (D) HCN 27. When a substance A reacts with water, it Ptoduces
AR
(c) Hro, (d) CH4 ttrt t,/- a conbustible gas B and 4 solution ofsubstance C
in water. Wben another subslance D reacts with
C
The critical lenlperature ofwater is higher than that this solution oI C, it Produces the sanle gas B on
of ()2 because lhe H2O Dolecule has
S
(d) F'ewer electrons than oxYgerl dilute sulphuric acid at rooDl teDlperature. A io]-
IA
Which of the follo\viog stalements is correc, 'f 2t. Whlch of the following pairs of su bstaDces on rcilc-
(n) Hydrogen has saDe ionization Potential as tion will not evolve II? gas I
alkali metals (a) Fe and H2SOa (aqueous)
(D) H- has saore electrooegativity as halogeDs (r) Copper and HCI (aqueous)
(c) H- has oxidation number of-l (c) Sodiunr and ethyl alcohol
(d) tl- will Dot be lberated at anode (d) lron aDd steam. c-B.s.D. nM.'1: 1re8
' \ I i ',r': 29. Acidifled solutioD of chromic acid on treatment
with H2O2 yields
What is hea\) water 'l
HlEo (b) Hl6o (a) cro3 + I-I2o + Oz (D) Crzo3 + H2o + ()2
(,? )
,Ar s wEr<-< d
ts. b 16. b 11. .l It. c 19, c 20. t 21. c 22. c 23, 24. a
25..1 26. b 27, a 2A. b
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111s2
Neut Course Chem istrrl
(c) CrOs + H2o (d) HzCtzOl + H2OtOz. (e) Dz (Ibrula M.E.E. 2002
:r1 P( r.I; l99tt which oDe of the following processqs will produca
pernlaDent hard water I
30, Anroogst H2O, HzS, HzSe and H2Tb , the one wih
(4) Addition of Na2S()4 to water
the highest boilioS Point is
(a) H2O because of hydrogen bonding (b) Saturation ofwaterwith CilCO3
(b) H21b because of higber molecular weighr (c) Saturation of water with MgCO3
(c) H2S because of hydroscD booding (d) Saturation ofwater with CaSOa
(d) precipirare cationic species 39. Comnrercial 1l'2 volunle H2Oz solution has a
N
tt r t. .!):j..
IA
molarity of
34. Action ofwater or dilute mineral acids on metals
IIT
15. Hydrogen molecules with excess eDer$/. 25. Multiply normality by 5.6. ie. 5'6 x I 5=8 4
-
A
29, c 30. 4 31, c 32. c J3.. -1J. r 35. d 36. b 37. b 3t. e
39. a
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HYDROGEN
1 1/s3
27.2Na+2H2O-H2+2NaOH 2 Ca2+ + Na2 [Naa (PO3)6] .-
ABC
a]Jd Zn+ 2NaOH 4 Na+ + Naz [(Ca2 (pO3)6]
DcB- complcx (solublc)
-NEZnOz+Hz
Sodiun hexameraphosphare-a polyphosphate, 35. Saturation of warerwilh CaSOa produces hardness
conbines with cations (ie., Ca2+, Mgz+) to form 39. Molarity = Volunre strength/l I .2
soluble complexes. =lt A1l 2-r'O
ADDTTTONAE gUEST|ONS
Aa se rt;i o n - Re a e on Ty p e e.u e sli o n s
.fhe foUowltrg quectto;;corJit oi t-. stat"tlerk n. Whllc anst erlng
these qu€stions, you arc requlred to choose ony one o
(a) lf both Assertlotr and Rcason sar hue aDd ahe Re{son ls o correct explanaflon
of the AssartloD.
(r) If both as.sertion alld Ressotr ore true but ReasoD is Dot a corrcct explanatiotr
of the Asserdor"
(c) IfAssertion is true but the Reosor b fclse. (d) fboth Assertior
and Ileason are false.
A.sscrtlon Reason
rrlhter is a gmd s6ive-Ef-nt
for ionic clmpouDds but Hydration e R cient enerry to
EE
poor for coyalent compounds. overcome la rogen bondi in
water while
AR
nds interact so
wcakly that even i€n der Uhals,forces between molecules
C
KM0O4 solution.
IA
H2O2 has higher boiling point tha[ r,!rter. The dipole moment of H2O2 is lirtle more than that of
IIT
Hzo'
The eleclronegativity differcoce betweel Be and H is very
high.
5. Its degree ofdissociarioD is high.
6. H2O2 on ioniccompound.
is (A.1.1.M.5.2003t
t.
llltylll9
S
l_194I4!?!
N
f. T 2. F; sod. polyrnetaPhosPhate 3. T
one is bolrde<l to SOI- ion by H-boDds 7. E Zn(OH), + 2NaOH -....-
IIT
4. Con'ccl reoton r The electroflggativity dilfcrencs 6, Coftecl rea.\on : The lone Pairs of electroos olt thc
betr{cen Bc (1 5) and H (2 1) issmall. O atoms are strongly attracted by ihc electronega-
t Coftect ossetlion : D2O is called heary water' tive Fatoms. As a re-sult,lone Pair-lone pair rePul-
sion ofthe two ory8en atoms is far less iD.O2F2 tban
Correctreaton: DDe to strooger D-O bonds, ttle
degree ofdissociation of D2O is lower lhan that of in H2O2. As a result, O-O) bond length is O2F2
H2O. (1 22A) is nruch shorter than in H2o2 (I 48A)
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r
e-Alock Elerr.er,ts
ol the
General inttoduction to sblock elernents-abundance, occurrcnce' anonElous ProPedbs
lirst elements in each gro.lp, diagonal relationship'
Alkali metals----occutrence, eleclronic conligurltion nd Physical. properties
(including lE, reactiiity and ]eactions with oryqen'
hydrogen, hal la. Basii natu roxides' halides' Li and
Na-otcurren and uses, NarCOa.
in atomic and Physical
proP
The R
EE
non-
Bi[lHl,E1":':j""Xilj
f alkaline earth metals-
AR
Mag ,
strlal uses ol lirne, lirne stonB' coment'
CaO
C
S
l,: :,r i, , r
,,:
:, , , . r: ,,1], , ]:
,
:,': j r: ,, :., , ,:
,:,
: r:, : j r:1
IA
tzll
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1212 Neul Course
element by weight in the earth,s crust. Sodium and 12.13. Diagonal r:latlonshlp.
magnesium are also present in relativety large
amounts in sea water, brine wells and a few silt . Some elements ofcertair groups in the second
period resemble with the certain elements of the
Iakes. Calcium and potassium also occur in sea
water but to smaller extents.
E5S.
I e.q
frHfi
frr-fi
Slmllar electronegatlviv Similar atomic and
lonic radii, Similar potadzing power
metals (Mg Ca, Sr and Ba).
FIGURE 12.1. llustration of diagonal rclationship.
chargc)(ionic 6izc). Polari6ilg parPlr h aldo 6omctimc6 hcs6urEd in tcrm6 of charge pcr u n it arEa, i.c
:z
J
(ioni. radius)'
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S.BLOCK ELEI\,4ENTS 1213
(iii) Similarity in polaising powel On moving (i) spodumene, LiA(SiO3)2, ald (ii)
lcpidolite,
across a period, the charge on thc ions increases LirAlr(SiOJ (FOH),. Sodium aad potassium are
and size decreases, causing the polarizing power to
the sevanth aI[id eighth most abundant elements by
increase. On moving down a group, the size in-
weight in the earth's crust. IiaCl and KCI occur in
creases and the polarizing power decreases. On
large amounts in sea water. The largest source of
moving diagonally, these two trends partly cancel
out. As a result, diagonally related elemcnts have
sodium is rock salt (NaCl). Other important
minerals of sodiumare: NarBoO, . L0 HrO (borax),
similar polarizing power and bence have similar
propertics. NarCOr. NaHCO3.z}{z0 (tona), NaNO, (clu7e
sl,l("il()\-l sdlt petre) and sodium sulphate (mimbilite) .
Lithium is the rlrir)y'y'tft most abundance ele- physical and chemical properties. The electronic
ment by weight in the earth's crust (lithosphere) configurations of alkali metals are given in Thble
C
Some important physical properties by alkali metals are given in Table 12.2.
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1214 llradc cyt's Neut Course Chem istt4l$[f
TARLE 12.2. Some phlsical properties r.rf gloup 1 elements (alkali metals)
Elements
I'roperty l,i Nn K Rb Cs l.r
(Radioxctive)
I llct roncgativity
(PaulinE scale) 0.98 0.93 0.82 0.82 o.'19
These proprties are briefly discussed below : conesponding atoms. However like atomic radii,
C
l. Inrge atomlc t dll. The anmic radii of these are the largest in their respective periods.
S
increase os we lravel down the group fum Li lost from the alkali metal atom, the monovalent
IA
,]7rcSe
to Cs as shorvn in Table 12.2 cation formed has one shell less than the cor-
IIT
Explanation. This is due to the reason that as responding metal atom. Further,with the loss ofone
hc atomic number increases, the number of energy electron, the effective nuclear charge increases and
shells increases by one with each succeeding ele- thus the remaining electrons are pulled closer to
nrcnt. As a result, the screening effect of the inner the nucleus thereby decreasing the size of each
lilled shells on the valence s-electron increases and individual energlshell. Hence, it can be concluded
lhc electron cloud tends to expand.In other words, lhat &te to contractive efrect oI lhe inueased nuclear
ths distance betweeeo the nucleus and the last shell chatge and lesser number of energ shells, the radii ol
increases and thus the atomic radius increasEs with cations are much smaller thon the conesponding
increase in atomic number. It may, however, be atoms.
stilted herc that asthe atomic number increases, the Thend ln the group. Like atomic radii, rfte
rrrrclcar charge alsogoes up. This ten& to deqease ionic radii increase we move down the group from Li
rhc atomic radii by attracting the electron cloud ro G primarily due to the addition of a new energy
inrvarrl more forcibly. But the screening effect is so shell with each succeeding element as shown in
li!r ge that it ovcrcomes the cotrtractiv€ effect of the Table 10.1.
irrcrcirscd nuclear charge. Hencc. the increase in 3. Low ionization enthalpies. 7-1rc ionizalion
,t ontic t tdius os we move down thc gtoup
from Li to enthalpies of the alkuli melals are the lowest a,\ com-
s is primaily due to the predaminstt soeening pared to the elements in the othet groups.
, il,'ct (addition of anew meryt shell ) of innerfrlled
Explanation, This is mainly because of the
tltclls on lhe valence s- electon.
fact that noble gas core shields the lone s-electron
2. Iarge ionic radll. The ionic mdii ol the in the valence shell from the direct attraction ofthe
, tttions fonned by them are smaller in ske than the
1
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S.BLOCK ELEMENTS 1215
positive charge on the atomic nucleus. As a result, metals, The metallic character increases down the
the valence s-electron is loosely held bythe nucleus group because ionization energ5r decreases down
and can be easily knocked off by supplying only a the group.
small amount of energy. The bigger the kernel or smaller the number
Thend ln the group. The ionbatian enthalpies of valence electrons, the weaker is the metallic
ol alkali metals decrease progressiely os we move bond.
down the group from Li to Cs. Since the atoms of alkali metals have bigger
Explanatlon. This is due to th€ fact that the kernels and smallcr number of valence electroDs,
s-electron to be removed becomes farther and far- the metallic bonds in them are very weak. Hence
ther away from the nucleus because oftbe addition they are soft and can be cut with a knife.
of a new shell with each succeedhg element (Li, 6. Meltlng and bolllngpoinls.The melting and
2rl ; Na,3rl ; I( 4sl ;Rb,5r1 ; Cs,6sl and Fr,7sl). boiling Wints of atkali metab are very low and
Due to an increase in tbe number of inner shells, decrease with inucase in atomic numbeti
the screening effect also increases. As a result, the
Explanatlon, As alkali metals have large size,
attraction of the nucleus for the valence s-electron
the intermetallic bonds in them are quite weak.
decreases and hence the ionization enthalpies
Hence they have low melting and boiling points
decrease as we travel down the group from Li to Cs.
which decrease down the group with the iocrease
4. +1 Oxidation state- Uniposldve lons. in the atomic size.
The alkali metals uhibit oxidation state of + I in
7. Naturc of bonds tormed. AU ,he alkali me-
their compounds and are strongly elect opositive in
tals Iom ionic (electovalent) compounds. The ionic
charactei The electopositive chaructet increases
character increases from Li lo Cs as we move down
from lithium down lo caesium in lhe gtoup. R
in thc group.
EE
Explanation. As the alkali metals have low
Explanation. This is because alkali metals
ioaization energies, they have a strong tendetrcl to
AR
gy. When these excitsd electrons returD to their element to lose electrons and hence stronger is the
ground states, they emit extra energy in form of reducing character or higher is the reactivity of the
electromagnetic radiations which fall in the visible elemsnt. Since the ionization cnthalpies of alkali
region thereby imparting a characteristic colour to metals decrease down the group, therefore, dreir
the flame. reducing character ot reactiviEt in the gaseous state
The colour actually arises from electronic increases from Li to Cs, i.e., Li < Na < K < Rb <
Cs.
transition-s in short lived species which are formed
momentarily in theflame. The flame is a rich source However, in aqueous solutions, it has been
of electrons, and in case of sodium, the ions are observed that the reducing character of alkali me-
temporarily reduced to atoms tals follows the sequence : Na < K < Rb < Cs <
Na+ + e-- Na Li. In other words, Li is the strongest while sodium
is the least poweful rcdrcing agent in aqueous solu'
The yellow flame of sodium commonly called
,ion. This may be explained in terms of electrode
sodium D-llne (actually consists of a doublet potentials (E) of alkali metals.
centred at 589.0 nm 539.6 "-) arises from the
"o6
electronic transitio rr3 s1 3 pt in sodium atoms
Electrode potential is a measure of the ten-
formed in the flame. It may - be noted here ahat the dency of an element to lose electronsi[ the aqueous
colours lrom differenl elements do not all arise from
solution. Thus, rnore negative is the electrode poten-
the sqme transition, or from the same species. For tial, highu is the tendenc! oI the elemenl to lose
example, crimson colour of lithium arises from a eleclmns and hence stronger is the rcducinB ogent-
short lived LiOH species formed in the flame. Siace tbe standard electrode potentials (E)
10. Photoelectrlc e[Iect. Alkali metals (escept of alkali metalsbecome more and more negative as
we move down the group from Na to Cs, therefore,
Li) exhibit photoelecffic effect. Photoelectic elfect R
reducing character of these elements increases in
EE
is the phenomenon of ejection or emission of
eleclrons from the melal suiaces when eleclromag-
the same order, i.e., Na to Cs. However, standard
AR
netic rodiations sre made lo strike against them. electrode potential of lithium, is the lowest, i.e.,
- 3. 04 volts. In othet wotds,lithium is the strongest
C
explained as follows.
eject electrons when elposed to light. It may be
IA
noted that lithium which has the highest ionization Electrode potential, among other things,
depends upon : (i) enthalp of sttblimatkn,
IIT
12.52. Reaction wlth uater. Sodium has a low melting point, and the heat
Alkali metals react with water, Iiberating H, and of the reactioD is sufficient to make it melt or even
forming their hydroxid es- The reaction becomes morc vaporize. The molten metal thus spreads out there-
qnd more iolent as we move down the gruup, Tltr:s, by exposing a larger su ace to water. As a result, it
lithium reacts gently, sodium melts on the surface of reacts even faster, gets evenhotter and catches fire.
water and the molten metal moves around vigorously Lithium, o! the other hand, has high melting point.
and may sometimes catch fue, potassium melts and Although the heat of the reaction is high, it is still
alwap catches fue and so are Rb aad Cs. Dot sufEcietrt to melt the metal and the hence the
reactioa proceeds gently. Other metals of thls
zLi + 2H2O .------.2 LiOH + H2 group with lower melting points react explosively
2Na*2HrO --+2NaOH+Hz with water.
2K+ zHzO '--.--r 2KOH + H, Rom the above discussion, we learn that ws
should be cautious while predicting the chemical
Because of their large negative reduction behaviour of elements on the basis of one single
potentials alkali metals are better reducing agents fundamental property ofatoms since in many cases
than hydrogen. Hence they react with compounds it rnay depend upon many other factors.
containing acidic hydrogen atoms such as water,
1253. Reaction with olrygen,
alcohol and acetylene liberating hydrogen gas.
The alkali metals tarnish in air due to the
2M +2 HrO -----------+ 2MOH +H2 formation of an oxide or hydroxide on the surface.
(Alkalimerals) Atkali metal
hydroxidc When heated in excess of air, alkali metals form
different types ofoxides depending upon the nature
2 M + 2qH5OH---------- 2 qH,OM + H2
of the metal, e.9.,
Alkali metal R
EE
cthoxidc Lithium whenheated in orygen forms lithium
M + HC = CH -C C- M+ +H2 monoxide (and some lithium peroxide).
--.....r M+
AR
2
=
Alkati metal acct,,tide 4Lt+O2 """""'- zLhO
C
Thns, lithium is the least reactive while the Sodium when heated with oxygen at about
S
reactivity of othet alkali metals towards water and 575 K forms mainly sodium peroxide (and some
N
575 K
Cause for low rcactivity of lithium. The low 2 Na * O, NuzOz
reactivity of lithium may be explahed as follows : --r Sodium peroxide
Standard electrode potential (E ) and Gibbs Olher alkali mecals, i.e.,I( Rb and Cs react
free energy (AG') are related by the equation, with orygen to form superoxides of the general
AG'= - nFE' formula, MO, whelg N4 : K, Rb and Cs, e.g.
wheren is the number of electrons lost by the
metal and F is the faraday constant. K+ 02 -----------. Koz
Potassium supeloxide
Since E for the reaction, Li+ (aq) + s-
U (s) has the lowest negative value, r'.e. - 3.04- { Thus the reartivily oI alkali metals with orygen
therefore, AG'ofthe reaction has the largest posi- increases down the group. Furthe4 the increasing
tive value. In olher words, this reaction does not stability of peroxide or superoxide, as the size of the
occur However, the reverse reaction, Li (r) -------' metal ion increases, is due to the stabilkation of
Li+ (aq) + e - has a large negative value of AG', so latger anions by lar4 cations through higJter lattice
Li liberates more enerry than any other alkali metal eneryies.
whenit reactswithHrO. Inview of this, atft st sight,
u
it appears surprising why Li reacts with HrO gently,
whereas Na, which liberates less energy, reacts Na
more vigorously and the hydrogen produced K
catches fire. The e:<planation for this observation Rb
lies in the kinetics (i.e., the rate at which the reac-
Ca
tion procceds) and not in the thermodynamics (i.e.,
the total amount of energy liberated) .
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1218 Ned Couvse
Explanatioo. Because of the small size, Li+ The order ol reoctivity of the olkali ttrctal;
has a soont positive freld arovrd it which attracts towards hydrogen decreases as we ntove down the
gtoup ftom Li to Cs. This is due to the reasott thqt the
lattice energies of thcse hydides <lecrease progres'
sively as the size o[ lhe ntelal cation inTesses and
thlts tlrc stobility ol these hydides decreases from
hand, Na+ ion because of its larger size than Li+
positive field around
LiH to CsH.
ion to combine with 1073 K
peroxide ion, Ol-.
ZLi+Hz 2 LiH
Lithiuor hFride
The larger, K+, Rb+ and Cs+ ions have still - 613 K
wcaker positive fields around them which cannot
2Na+H2 .._ 2NaH
Sodium hydride
preveni even peroxide ion, O!- to combine with
Alt the alkali metal hydrides are ionic solids
atrother orygen atom to form suPeroxide, Ot. with high melting points.
7/202 02 Since these hydrides contain the hydride ion
02- .-.---.--------- 20; (H-), therefore, they liberate hydrogen at the
oxidc Pcrqidc supcaoxide anode on electrolysis.
It may be pointed out here that superoxide ion All these hydrides react with proton donors
such as water, alcohols, gaseous ammonia and
J:O
r O :)- has a thrce elecion bon4 i.e., it hos alkynes liberating H, gas.
one unpaired elecfron which makes it coloured
(LiO2, NaO, are yellow, KO, is orange, RbO, is LiH (s) + Hzo (0 ......._ LioH (aq) + H2@)
R
NaH (s) + ROH O --"""'r RoNa (s) + H2 @)
EE
browrr and CsO, is orangc) and Parumagnetic-
Sodium peroxide is ycllow in colour probably due Hcat
AR
to the presence of a small amount of superoxide in NaH (s) + NH, @) ..........* NaNHI (s) + H2 @)
C
AII the alkali metals on expcure to atmosPhere hydrogen for military purposes and for filling
IIT
All alkali metals dissolve in liquid aounonia AII the compounds of alkali metals are
(solubiliry may be as high as 5 M) giing higlty predomirantly ionic. Some of the general charac-
conducting deep blue solutions. teristics of these compounds are discussed below :
Eryrlanatlon. These solutions contain am- 12,5.1. Oxidcs and Hydroxldes
moniated cations aod ammoniated electrons as All the alkali metals, their oxides, peroxides
shown below : and superoxides readily dissolve in water to
1 M+(.r +),) NH3-----.r M+(NH3), +e-(NHr), produc€ corresponding bydroxides which are
strong alkalles, e.9.,
When ordinary light falls on ttrese am-
moniated electrorx, they get excited to higher levels
2 Na+ 2 HzO-.-....| 2 NaOH + H2
by absorbing energy corresponding to red region of NqO + HrO .----------r 2 NaOH
the visible light. As a result, trarsmitted light is blue
which imparts blue colour to the solution. Some
NarO,+2HrO -.-.....r 2NaOH * HzOz
important properties of blue solutions of alkali R
2KO2+2H7O 12KOH + H2O2 + ()2
EE
metals in liquid ammonia are as under :
Thug peroxides and supcroxides also act as
AR
(i) Dilute solutions of alkali metals in liquid axidbing agent since they react with HrO forming
C
to copper-bronze and the solutions acquire metal- The hydroxides of all the alkali metals arc
IA
lic lustre due to formation of metal ion clusters. white crystalline solids. Thcy are strongest of all
IIT
(ri) The blue coloured solutions areparurzca" bases and readily dissohe in water with the evolu-
netic due to the presence of large number of un- tion of much heat. A number of hydrates of the
paired electrons but bronze solutions are heavicr alkali metal hydroxidas e.g., NaOH, Hz()
diamagnetic due to formation of electron clusters (where n = 1,2,3,4,5 and )
have been preparcd
in which ammoniated electrons witb opposite spin from their aqueous solutions but little is known
group together, r'.€., about their structures.
2e- (NHr)r-------r I I e- (NH:)rl I J e- (NHr)rl (i) Basic swngh. The basic strength of thosc
(iri) The solutions of alkali metals in liquid hydroxides increases as we movc down thc group
from Li to G. Thus, NaOH is a stronger alkali than
ammonia are good conductors of electricity due to
the presence of ammoniated cations and am- LiOH ; I(OH is a stronger alkali than NaOH ancl
moniated electrons. However, the conductivity so oD.
decreases as the concentration increases sincc the
ammoniated metol cations are bornd by he fue UOH
unpaired electrolos $)hich have been descrbetl as \,laot
extr and€d metals.
(lv) These solutions are stronger reducing
KOH 2i,6
agents than hydrogen and hence will reacf with bz
water to liberate hydrogen.
(v) In preseace of inpurities or catal)6t such
Explanation. The hydroxides of alkali metals
as Fe, the blue coloured solutions dccompose to
behave as strong bases due to their low ionizqtion
form metal amides with the liberation of Hr.
€ner8r'er. Due to low ionization energies, the M O
-
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12110
atse ChcmiswsfrBlD
bond in M
()H - ions.
- O - H can easily break giving M+ and
MOH ....- M+ + OH- (basic narure)
M+ x-
o6)
C
S
N
MOH + HX
IIT
_._.!icl > NsCt > KCI > RbCt > CsCl Thus,
LiCl is more covalent than KCl.
ilnip iz.i.'S
(in kl mo
;i;; (7) Slze o-fthe arllor
_,_s potarizability.
ts !-arycr the at on, greqter
This explains why coval eni char_
acter oflithium halides is in the order
Li 4tz LiI>LiBr>UCl>LiF
-398 -350 -2'11
Na ,_ _F9r
tle samc reason, dipole moment of LiI
-569 -400 -360 -2A8 -
(o.25 D).is much less than the theoretically ex_
K -563 424 -392 pected value of 11.5 D ifit were l\OVa ioltc.
-3U
Rb -549 423
Cs -531 4U
-389 -329 . (rr) Charge on the ton. Greater the chop on
the catio4 Water is its poloizing power
-395 -337 and .lience
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S-BLOCK ELEMENTS 12/11
larger is the covalent character. That is why the (c) Hydration cnthalpy. It is the amount of
covalcnt character ofsome of l.he halides increases enthalpy released when one mole of gaseous ions
in the order Na+Cl- < Mg3+Cl2 .
Alr*Clr. combine with water to form hydrated ions.
Similarly, greater the charge otr the adon, M* G) + aq M+ (aq) + hydration enthaipy
morc easily it gets polarized thereby irnparting x- (g) + aq --'-'+ x- (aq) + hydration enthalpy
morc covalent character to the compound formed. Higfier the hydrolion enthalp, of the ions",
For example, covalent character increases ia the greotcr is tle solubilily oI the enthalry in water
order : NaCl < NarSOo < NarPO. as the size of Further, the odeDt of hydration depends upon
the aniou increases and hence larger is the covalent the size of the ion. Smaller the fie of the ion, more
characler Thus, the covalent characlet decreases es higbly it is hydrated and hence greater is its hydrated
the size oI the anion decreases- ionic radius and less is ils ionic mobility (conduc-
tance) . Thus the order of their radii and mobility are
(iv) Electronic configuration ofthe cation. If
two cations have the same charge and size, the one Ionic radius : Li+ < Na+ < K+ < Rb+ < Cs+
with apseudo noble gas configumtion, i.e., having 18 (in pm) 76 r38 152 167
electrons in the outermost shell has greater polariz- Hyd.ration
ing power than a cation with noble gas configura-
tion, r'.e., having 8 electrons itr the outermost shell.
rrumberar' 25'3 16.6 10.5 10.0 9.9
For this reaction, CuCl is more coralent that NaCl Hydroted
(although Na+ and Cu+ have same charge uiz +L rochus: Lr' >Na+>K+>Rb+>cs+
and nearly the same size ra'z Na+ (1'02 A) and (inprn) 3q n6 2i2 2U Z2A
cu+ (0.96 A).
Ionic mobility : Li+ <Na+<K+<Rb+<cs+
(D) latfice €nthslples. Latticr etrthalpy is
(ar R
ntfnite 33 43.5 64.5 67.5 68
EE
5
defined as the amount of enerry required to
separate one mole ofsolid ionic compound into its dilution)
AR
gaseous ions. Er4zenlly greater lhe lattice enthalpy, In the light of above argumentE let us now
C
higher is the melting point oI the alkali metal halide explain the melting points of alkali metal halides and
their solubility in water or organic solvents. Thug
S
r\BLE l.ai(i.:..nri'iipi-i. t'f,ir,,ii ,i' .'-' (i) A delicate balance between lattice enthal-
IA
12.4.
thalpies (in kl mol- r). (sohrhilitie\ (in /l{)0 g
IIT
of lithium hqlides are lower than those of the cor- I (alkali metals) differs from rest ofthe elemcnts of
responding sodiwn halides and thereafier they this group in many rcspects cotrtrary to the expec-
C
decrease as we move dowtt the goup ltom Na to Cs. tations. Thb anmlous bchavina.o{Iithhqi*drc -
S
N
(887 K) as compored to that of NaCl is prubably (i) vcry suaE eine of lithium atom aad its im.
IIT
(iv) Lithium combines with nitrogen to form (ry) Lithium ion, being very small in size, is
nitride while other alkali metals do not very strongly hydrated in aqueous solution than
6Li+N2 -* 2Li:N other alkali metals ions that is whv effective size of
Li+ ion in aqueous solution is thjlargest.
(v) LiOH is a weak base *hile the hydroxides
of other alkali metats are strong bases. 12.8. Diagonal relationship ol
Lithium with Magnesium ii:i-:r::iiii+,1irr+:ri:i.r:.i:riiir:::":
(yi) Lithium hydroxide on heating dccom-
poses to form lithium oxide while othc.r alkalimetal Lithium resembles magnesium mainly
hydroxides do rot due to the similarity in sizes of the ir atoms (Li :
2 LiOH ---------* Li2O + H2o 152 pm, Mg : 160 pm) and ions (Li+ = 76 pm,
(wi) Lithium carbonate* on heating dccom-
Md+ = 72 pm). The main points of similarity are :
poses to give CO, while other alkali metal car'- (i) Both LiOH and Mg(OH), are weak bases.
Na+ -C = C- Nil* + H2 A
LirCO, ........_ Li2O + CO2
C
Disodium acetvlide
However, when Li is heated with carboo, it A
S
other alkalimetals do notreactwith carbon directly (iu) Both Lithium and magnesium do not form
IIT
A solid bicarbonates.
ZLi+ZC + Li+ -C = C- Li+ (v) LirO and MgO do not combine withexcess
Dililhium acctylide
(x) Lithium nitrate on heating decomposes to of orygen to give a peroxide or a superoxide.
give LirO, NO, and O, while other alkali metal (ur) Both lithium and magnesium nitrates
nitrates decompose to give the corrcsponding decomposc on heating producing nitrogen dioxide.
A
nitrite and orygen 4 LiNO, '------r / li2o + 4 NO2 + ()2
4 LiNO3 """""'r 2 Li2O + 4 NOz + O2 A
2 NaNO, ...._ 2 NaNO, * O, 2 Mg(NOr),
---+ 2MgO + 4 NO, + O,
(ri) The oxide, hydroxide, carbonate, phos- (vii) The hydroxides, carbonates and fluorides
phate and fluoride of lithium are sparingly solublc of both lithium and magnesium are sparingly
in water whereas the corresponding salts ol other soluble in wa.er.
alkali metals are soluble in water (vrii) Because of covalent character LiCl and
MgC[, are soluble in ethanol.
(xi) Because of covalent character, halidcs of
lithium (like LiCl) are soluble in organic solvents (u) Both lithium perchlorate and magnesium
while those of other alkali metals are i-nsoluble. perchlorate are highly soluble in ethanol.
(.rn'i) LiCl is deliqucscent and crystallizes as a (-r) LiCI and MgCl, are deliquescent and crys-
hydrate, LiCl.2HrO, whereas other alkali metal tallise from aqueous solution as hydrates,
chlorides do not form hydratcs. LiCl.2 HrO and MgCL.6 H2O.
Li-o\
.Strucrure of Li2CO3 is C
li-o,/
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12114
llrtttit'r rt's Neut Coprse ChemistrqWID
-' t.
l:ili MonoxtdGq peroxirlcs and suPcrodd€s of alkali metat& All the flve alkali mctals can be induced to form
normat cidis (r'.€. moncddes), permides aod superoxides by dissoMng the mctal in liquid ammonia and
bubbling in the approPriate amount of o)(ygen.
:jii 2. Ctl6td;tructurti olmonoddcs olalkall mctals ExcePl Cs2O which has anti-Cdcl2laycr structure, all other
monoxides, ie., Li2O, Na2O, K2O and Rb2O have anti-fluorite structures.
,ri -1. FotrsshE supctordde (Kor) isus€d asa sourEc ofoxygen in subElarincs, sPacEshuttlcs and inemergcDcy breathing
appamtus suci s @O,B?l ,narb. Such rDast6 are used in resqre work in miD€s aod in other areas wbere the air is so
Aihcient in ulrgcn that 8n artifcial atmosphere must be generated. The moisture of the &eath reacts with
superside to liberate Gygeq and at tbe same time the potasium h)drcldde formed remo\€s carboo diodde as it
is odaled thereby alo ing the atmccphere io lhe mask !o be continuousy regenerated.
4KO, (s) + 2 H2O 6) 4KOH (4q\ + 3 o2gt i KOH (44) + coz G)+ KHCO3 (s)
-
with Co2 forming lqco3 and with co2 and the moisture forming KHco3.
KO2 also combines directly
4Y'o2+ 2co2 a2l$Co3+3oz; 4Koz+4co2+2H2o 4KHco3+3o2
,.ii' :l Potssslum ozoDlde (Ko3) is formed when ozone is Passed tbrough KOH.
-
2KOH + 503 2KO: + 5 o, + H2o
-
It is an orange coloured solid and contaiDs the paramagnctic Ot ion. R
EE
::,:r !i. Uthlum hldroide (UOII) bused to remc've CO2 from exhaled air in contined quaflerslike submarines and
AR
sPac€ vehicles.
,,r,i 6. fbe alkali m etals rcact uritb, halogens and inlerhologen CI,mpounds formi[S lonlc polyhalide compounds.
C
KI+ Iz KlI3l
S
-
N
KF+BrF, K[BrFll
IIT
-
solutio[ of alkali metals such as Li, Na or K in
' ? The
r:iii; on of ethylenic double
bonds, acetylenic triple bonds to double bonds and me Birch reductlon.
r,,i 8 Lithium is lhe li8hlcst knol n metal, having deDsity be, stored i[l keroseDe
oil becausc it floats otl the surfac€, It is kePl wrapped in Parafhfl wax.
,i!ti 9. C.s is the mc! electroPositive elcment due to its lowest ioniztion enerry.
,,i | ,r Uthium canDot bc used in makiDg photoelectric crlls b€cause out of all the alkali metals, it has highest
ionization enersr and canDot emit elcctroDs when exposed to light.
,il IIThe compounds ofalkali metals are mlourless (unless the anion is coloured like permangaDate or dichromate)
.
and diamagnetic. Thls is because they have noble gas coDfiguraton with no unPaired electroD.
t;i:t 12. The pcrfiides ofalkali metab arc colourless and diamagneticwhilesuper idcs are paramagnetic aod colouM.
iiiir l-1. All alkali meta.ls exist as body-c€ntred cubic lattice with a coordinatioD number of8.
,ti l.{. Due to small size, lithium does not form alums.
:,,l ti. Alkali metals combiDe $rth mercllry to form compouDds kno n as AmalSams. This readiolr is hiShly oothermic.
1;1.9. Lithium i!:..lliit;i:;r,iii:i:;ir:iii:i:!t:jri:ii:j:iin:i:i:rj:t:.:.:iL.iii,tiir.:iiiii:ij:j mineral is alWays small and thUS extraCtiOn of the
so easv' some importa minerals of
Lithirun is the tust member of alkali m" illilXltJ::
tals. It is the lightest metal known. Mhcrals of.,thtum
12.9.1. Occurrence. (i) Spodumene, LiAl(SiO3)z containing 4-
67o lithium'
Lithium is the thirty-frfth most abundant ele-
ment by weight in the earih,s crust. It mainly occurs Qi) Triphylite, (Li, Na)rPOn.(Fe, Mn)r(POo),
as silicate minerals but the amount present in any containing upto 47o lithium.
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S-BLOCK ELEI\,4ENTS 12115
(iii) Petalite, LiA(Si2O5)1 containing 2.7- (SiOr). The ftltrate thus obtained is treated with a
3'7Vo lithilum. calculated amount of NqCO, to precipitate
(iv) Lepidolite, (Li, Na, K), (SiO3)3 €OH)2 aluminium and iron as carbonates which are fil-
containing 1. 57o lithium. tered off. Excess of NarCO, is then added to the
(v) A mbtygonitc, LiA(PO1)F. ftltrate to precipitate LirCOr. This is filtered and
dissolved in HCI to obtain LiCl which is purihed by
Lithium also occurs in certain spring waters
and insome plantssuch as tobacro, beat and sugar- cxtraction with alcohol.
cane. In India, Iithium is mainly found as lepidolite (ii) Fuslon method. The powdered silicate
in Bihar, Rajasthan, Karnatka and Kashmir. mineral is fused with CaCO, and the fused mass is
12.92. Dilliculties encount€r€d during ex- extracted with HCI and filtered. The filtrate con-
traction of alkali metals. tains chlorides of Li, Al, Ca, Na and K whereas
Alkali metals, cannot be extracted from their silicon is removed as insoluble residue. The filtrate
ores by the usual methods of extraction of metals is evaporated to dryness and the residue is ex-
becausc of thc following difhculties :
tracted with pyddine in which only LiCl dissolves.
Pyridine is distilled offwhite LiCl is leftbehind. The
(i) Alkali metals are strong reducing qgents and
method discussed above may be summed up in the
hence can tot be &rocted, by reduction of their oides following flow-sheet.
or chloides.
(ii) Alkali metals being higltly electropositive Lithium ore (Spod,rmene or l,epidolite)
cannot be displaced from the aqueous solutions of Flrse with CaCO3,
tluir sahs by otlrct rnetals.
Hcl
(iii) Alkali metals csnnot be isolated by R and enract with and filter
EE
electt olyis oftlrc aqueous solution oI their salts since
AR
nwtals are much higlwr than that of tlrc lrydmg*. Evaporate to dryness aod
S
IDs-oluble
mercury to form an amalgam from which its (LiCD
rccovery is very difficult. flacl, KCl, CaCl2, AICI3)
GRAPHITE
ANODE
BRICK I /ORK
STEEL
CATHODE
is 9970 pure and is preserved bykeeping it wrapped in air or orygen at about 375 K, it burns with a
R
EE
in paraffin wax. It may be noted here thal lithiunt brilliant white light forming lithium monoxide,
being the lighest metal known (cknsity :
g' 5j4 t Li2o
AR
cm-3) cannot be stored in kerosene oil since il llodls 4Li + Oz '------' zLiko
C
on the surface.
S
(b) eat tcnsile Out of these minerals only NaCl has been used
econoEically to exEact thc metal and /rence NaCl
S
strength steel lt is
N
(c)
extremely tough rs Sodium is extracted by the electrolpis of
used for armour ts' fused sodium chloride by a process called Down's
(rI) It is used for producing thermonuclear Proccss,
energr iequired for propelling rockets and guided Dllliculties encountered Although sodium
missiles. chloride is very cheap and h abundantly available
or scavcnger vet the derclopme tt of Down's process for the ex'
since and nitrogen' iraction of sodium ftom fused sodium chloride was
Thus ces of orygen delayed because of the following reasons :
and nitrogen during refining of metals such as cop- (i) Sodium chloide melts o. Im4 K ad it is
per and nickel. difrcufi to afrain and maintain this high lempemture'
Gv\ Lithium corbonate is used in making a (ii\ Sodiwn boih at about I 156 K and hence at
speciil variety of glass which is very strong and is rhe temperanre of electrolysis, the melal liberuted
weather proof. will vaporise.
(v\ Lithium chtoidz s used iu air-condition' (iii) Molten sodiwn fotms a metallic fog (col'
ing ptants to regulate the humidity. lt is also used io loidal sohttion) with fitsed sodium chloide'
Ni-Fe accumulators. $v\ The pruducas of eleclrolysis, sodium and
(i) Lithium bimide is used in medicine as chloiii, corride the mateial of the cell at this high
sedative. temPerufrua.
Mi'l Lithiun bkaftonote and lithium salicy In 194, J.C. Down overcane all these diffrcul-
,ate havi been used for treatment of rheumatism ties. He observed that the addition of calcium
since the resulting lithium urate is soluble in water'
v
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12118 Pradeep,s
chloride and potassium fluoride lower the
melting
point of sodium chloride to g50_E75 K. CH LORiN E
Cl- "'-.----+ Cl + e-
CI + Cl ..........- Cl2
Adyantages of Donn,s proc€ss.
R
EE
(i) Sodium metal obtained is of high purity
(abo* 99 5%) .
AR
.
product.
IA
_,^
place than Costner,s
dunng electrolysis are : prorcss rnvolving electrolysis of fused
Dissociation sodium
Nacl .....-...- Na+ + cl-
hydroxide.
A'KN,@, irE
:;l;l: ii::;:iil i:lii::i,tr :,:i
KOH--g+1gq-
Aa cathode :
K++e-*11
At orode :
4OH-- C,2+2HzO+4e-
2. Reductlon ofKCI with so.liunr.
Potassium can arso be obtained by reduction
ofKCrlvith Na vapoun at about I125I( in a large f.ctiona ng corumn.
KCI +Na _ NaCl +K
Potsssium thus obtai[ed is about 99.5%
pure
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S.BLOCK ELEMENTS
12119
Pb(CrHr)n whiclr is used as an anti-kttocking sqent heated to give pure sodium carbonate. Recrystal-
lization fr-om water produces washing soda,
for gasoline. Na2CO3.10 HrO.
@ Liquid Na or its alloy with potassium is NECO3 + CO2 + HzO ---"'r 2 NaHCOT
usetl as a coolant in nuclear reactors.
(r'i) lt is used in lhe manufacture ofnumber ol' 2 NaHCo, '-""+ NazCor + H2o + CO2
chemicals such as Na2or, NaCN and NaNHr' Function of ammonla. COz is only slightly
(uii) Sodium is used in sodium vapour lamps' soluble in water. ds a result, the conccntration of
is largcly used in industry for the
(viii) Sodium HrCO, is very low. Further since H2CO3 is a very
protlucrior: oI artiFrcial rubber, dyes, drugs etc' weak acid, the concentration of HCO3- in the reac-
(r-r) Because o[ its lightness and high thermal
tion mixture is extremelY low.
concluctivity, it is used for filling exhaust valves of :. H2CO3 ...(r)
co2 + H2O
aeropiane engines.
a9ii!9 1..l:: :'i1 1" h' Na2c o:' H2CO3 : H+ + HCO; ...(r,
1
i:l i:-s'- 9 ::l
:
Sodium carbonate commonly known as To shift the equilibrium in the forward direc-
wqr;hing soda is manufactured by Solvoy amnronio tion, a base such ai NH, is used which combines
process.
with H+ to form NH.+ ion.
H+ + NH3 ----' NHr
Thus the function of NH3 is to Produce a
R
EE
solution.
sufficient amount of HCO! ion which enables
sparingly solubleNaHCO, to precipitate out ofthe
AR
Out oI the various compounds possible, (c) D€talls of the process. The manufacturing
S
lizes out. This is finally calcined to form sodium details the Solvay ammonia Proc€ss are
IA
'Non-ev.rluatiw.
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S-BLOCK ELEMENTS
12/21
NH-1
produce NHr. Therefore, except for small losses,
NaHCO,(s) +
C
NHoCt (ag)
no additional NH, is required.
S
(iii) Filtration. The solution flowing out of the NaHCO3 to NarCO, acmrding to reaction (iri) is
IIT
carbona(ion lowcr contains tiny crystals of sodium reintroduced in the carbonation lower.
bicarbonate. These are fiItered by passing through Thus, NaCI and CaCO3 are rhe only raw
vacuum ttlters.
materiallused which are quite cheap. At the same
(iv) Calcination ofsodium bicarbonates. The time CaCl2 is produced asa bye product which, of
sodium bicarbonate obtained above is heated
course, has no large scale
strongly or calcined in a kiln when sodium car_ Thus, solay ammonia oroc
bonate is formcd. tiuuous and self-contained
2 + CO2 + H2O
NaHCO, -------+ NarCg,
(v) Ammonia recovery tower. The filtrate
from the carbonation tower contains ammonium
chloride and a little ammonium bicarbonate It is
made to flow down the ammonia recovery tower
while a current of steam is matlc [o go up. Vilk of
lime is introduced at a point little above Ge middle
of the tower. Ammonium bicarbonate is decom-
posccl by steam anrl ammonium chloritle by milk of
limc as lollorvs :
Hcat
NH4HCOT -------. NH3 + CO2 + HzO
decompose further'
C
Elcctronic
Sr Ba Ra
IIT
follows R
EE
:
(i) The divalent cations of alkaline earth me-
AR
C.mpaLis.n nf .t,rng", i" ,n" n,.-rrr,,, nr*li ,",r l,r,i ir*ii, tr.,l
"n..gy "i
MgCl (aq) aH(tiJrnot-l) MgcL (.rr) A H (kJ nlot--l)
-7?4
5. Elec-tropositive or Metaltic character The
C
S
N
IA
IIT
. On
rncrease
p, the atomic radii
s decrease. Conse_
quently, metallic character
mcreases.
tion enersv decreases. Beryllium forms covalent alkali metals, therefore, alkqlifle earth metals ate
lcss reactive thon coresponding alkuli metals'
compoun;s because iL has smaller size and high
ionization energY. 12.15.1, Realucing character.
The alksline earth metals are weaker reducing
aeents than the alkali metels. Like alkali metsls'
tieir reducing chdracter also increases down the
lattice.
9. Flame colouration Akaline earth metals
intpafl a characterislic colour to the llame'
Calcium Strontium Barium Radium
Brick red Cimson Apple gzen Cimson'
Be to Ba.
R
EE
AR
C
7nK
2 SrO + O, SrO2
12.153. Reaction with air (uitrogrn anrl high prEssurc
nrlgen) SrO, b prepared in a similar way but under
R --
highpressure aod temperature. CaO2 isnot formed
EE
lium
form lhk yry^blr_ 9"1 be prepared as rhe hydrale by
AR
e of
beryllium oxide Ca(OH), + HrO, .......r CaOr.2HrO
S
ride
N
(B%Nr)
Crude MgO, has been made using HrO, but
IA
It is an iozic compound and reacts with water the formation of metal clusters.
Thqse solutions decompose very slowly form-
C
forming methane
BerC+4HrO ' 2Be(OH)z + CH+ ing amidas and evolving Ur, but ttre reaction is
S
N
Sr compounds.
IIT
which are less ionic than the corresponding com- BeCI, + 2NaOH-r Be(OH), [ +2NaCl
pounds of the alkali metals. Usually tbe cxides and
other salts of Be and Mg are rnore covalent than MgSOa +2NaOH +
Mg(OH), J + NahSO4
those formed by the heavier and larger members Properties of hydroxides. (i) Basic chuackr.
(Ca, Sr, Ba). A general survey of some of their Due to small size and high ionization enthalpy,
compounds is presented below. Be(OH), is amphoteric. It, therefore, dissoGs
12.16.1. O)ddes and Hy&oxides both in acids and bases.
Oxides. The oxides of alkaliae earth metaLs Be(OH), + 2HCl r BeCt + 2HzO
MO, are obtained either by heating the meta.ts itr
diorygen or by thermal decomposition of their car- Be(OH), + 2 NaOH......+ NarBeO2 + 2 H2O
bonates. Sod. beryllatc
A or Be(OH), + 2 OH- + [Be(OH)a]z-
2M+02 r2MO (M =Be,MgCa) Bcryllatc ion
A The hydroxides of Mg, Ca, Sr and Ba are
MCO3 ""'* MO + CO2
basic. Their basic strength increases as we move
(M : Be, Mg C4 Sr, Ba) down the group. This is because increase in their
Except BeO, all the oxides have rock-sa-lt sizes and decrease of their ionization energies
structures. Rrther, the enthalpies of formation of weaken the strength of M-O bonds in trlOH
these oxides are quite high and consequently they which ultimately breaks to give OH- ions and thus
are very stable. increase the basic strength.
Metal o(ide However, these hydroxides are less basic than
BcO Mso C.ao SrO BaO
A/ I' (kJ nrol -l) 550 590 62i 5m 5,15
R hydroxides because
EE
I
smaller ionic sizes
AR
are chemicallyinert and act as electrical insulators. hydroxides are less soluble in watsr as compared to
S
Because of these properties, these oxides aro used the alkali metal hydroxides.
N
for lining furnances and hence are used as refrac- The solubility of tbe alkaline earth metal
IA
tory materials. Due to small size of beryllium ion, hydroxidesin water increases with i.ncrease in
IIT
form hvdrates but their tendency to form hydrates CaCl, SrCl, BaCl,
decreases. For examPle, MgClr'6 H2O,
C
below :
compated to NaCUice at 255 IC It is also used as a ever the hydration encrry decrcases from
desiccant (drying agent in the laboratory). Bez+ to Ba2+ appreciably as the size ofthe cation
(iii) Anhydrous MgCl, is used in the iucreases down the grottp. Hence, the sohrbilities oI
electrolyte extraction of magnesium. sulphates ol alkaline eafth metab deoease down the
gmup nzinly &te to
12.17. Solubility and Therrnal
Stability o, Oxo Salts lrom B*+ toBaz+.
MgSOois due to he high hydration mergies due to
The salts containing one or more atoms of smaller Bd+ and Mf+ ions.
oxygensuch carbonates, (iii) Stability. The sulphates of alkaline earth
bicarbonates, tes oxalates metaf,s decompose on heating giving the oxides and
and phosphat Let us now
discuss the solubility and thermal stability of some
sor.
of the oxo salts of alkaline earth metals. A
MSOa """- MO + SO3
12.17.1. Sulphates.
The sulphates of alkaline earth The temperature of decomposition of these
metals
(MSO.) are prepared by the action of sulphuric sulphates increases as the basicity of the hydroxide
of the corresponding metal inireases d-own the
acid on metals, metal oxides, hydroxides and car- group. For example,
bonates.
M + H2SOI """"'- MSOr + Hz Compunds: BeSOI MgSOa CaSOr SrSO.
MO + H2SO1 ..-.---. MSO. + H2O Temp. of
(i) The sulphates of alkaline earth metals are tion ofSO!- ions.
S
N
all white solids. Berylliuq magnesium and callium (rr) BaSOoii both insoluble in HrO and opa-
IA
MgS04
=6
z2
as white precipitates when
(i) calculated amount of carbon dioxide is
CaSOa 6 a0 passed through the solution of the alkaline metal
l!o hydroxides
Q>
SrSOa
M(oH)r(aq)+Coz (8).......' MCor(s) + H2o(4
;!c
BaSO. 3ur and (ii) sodium or ammonium carbonate is
added to the solution of the alkaline earthmetal salt
(ii) Solubility. The solubiliry ofrhe sulphares such as CaC!
in water decreases down the group, i.e. Be'> Mg
Caclz @4 + NarCO, (cq)
> > Ca > Sr > Ba. Thus, BeSOo and MgSOn are
highly soluble, CaSOo is sparingly soluble but the -......-. CaCOr (s) + 2 NaCl (aq)
sulphates of Sr, Ba and Ra are virtually insoluble.
Explanatlon. The magnitude of the lattice
energy remains almost constant as the sulphate is
are
ltYd
,fll.TlJfJT;
hydraied ion
so big that small increase in the size of the cations [B" and hencc is
from Be to Ba does not make any difference. How- precipitated only in an atmosphere of COr.
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prn41' 1' 7r'5 Ne.4 Coulse thcmistqlifrlD
12132
BeCO3 MECO3 CaCO3 SrCO3 BaCO3
B6CO3 <373K 813 K 1171K 1563 K 1633 K
MgCos k*
oaE
BeCO, is thus unstablo and can be kept onty
CacO3 IUJ
ir, o in an atmosphere of COr'
srCo3
o iil Bicarbonates. The bicarbonates of alkaline
gE earth metats are prepared by passing CO2 tbrough
BaCO3
a suspension of metal carbonates in water'
NH4OH.
of
(r'i) The solublo carbonates, i e', carbonates
C
follJws :'
and the
S
its group.
IA
of lheir
(ri) It has higher melting and boiling points
IIT
than the other members. Some points o[ similarity are given below :
( ) Beryllium does not react with water ev€n ve a tendeucy to form
at high temperatures while othcr mctals do, c.g.,
the cblorides ofboth (i.e.
Mg + H2O MgO + Hz cova-lent are soluble in
(Boilins)
(rv)
-' organic solvents.
(ri) Both BeCl and A.lCt, act as strong Lewis
(because
acids.
poladzin
ionic compounds. (ur) Both BeCl, and AICI, have bridged
Because of covalent character, salts of beryl- chloride structures in the vapour phase.
Iium are easily hydrolysed. For example, CI. CI .CI CI
_. _/ \- \./
BeCO, *
HrO.---r [B€(HrO).|2+ + CO3-
4
Cl-Be- Be-Cl Al \./'-Al
(v) Beryllium oxide and hydroxide are am- \",/ ,/\,/\
photeric whereas oxides of other alkaline earth CI CI CI
metals are basic.
BeO + 2 HCI ..........- BeClz + HzO
BeO + 2NaOH ---+ Na2BeO2 + HzO
Sod. bcrr atc
(vr) Carbides of Be(BqC and BeCr) are
covalent (e.g, Be = C = Be) whereas carbides of
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Net4 Cttttrse Chenr istr4
12134
(vi) The oxides and hydroxides ofboth Be and Be2C 4H2O ' 2 Bo(OH)z + CHr
+
Al aie amnhoteric and dissolve sodium in ALq + uH2O ,4AI(OH)3 + 3CH4
iua.nxide soiution as well as in hydrochloric acid' (eiii) Salts of both these elements lorm
BeO + 2 HCt ----"* BeClz * HzO t ydrui"d' ions e.8., [Be(OHr)nlz+
and
iii:ti:lii.r:i::iil.:ij:l::iii:lii::iilIil:i;ii::l(:liii:i'ii;ii'6i:-iiiii:i;::.:i:i':;'jliiii'iiiJ:iII;''ii':iii3r1,li:lli:iiiijiii:i:i';
APD R,K
::l.Thecon]poundsofalkalineearlhmelalsinwhichrhemetalisdittslentarcdiamaSneticandcolourlessunless
' with no unpaired electrons'
,rr. #rrii. Thls is tecausc itrey trave notle gas configuration
""toured. most ofthe barium compounds are made from
ili;'i 2. Reduction ofsulPhateswith carboo givessulphides Therefore' R
EE
barium sulPhate.
auur*oao
AR
Basoa+4c
C
.:i:j3'MaSnesiumpercblorate(Mgclo4)isusedasadryingageotcalledanhydrone.
S
N
IA
2. Flom sea water. The sea water cotrtainitrg At anode: Cl- Cl+e-
magnesium chloride and magnesium sulphate. is -""'
Cl + Cl ---.-.r Cl2.
concentrated under the sun and is treated with
slaked lime, ca(oH)2. chlorine liberated at the anode passes o.ut
ftom the exist Drovided in the porcelain tube while
MgCl, + Ca(OH)2 """'r Mg(OH), + CaCl, the magnesiurir liberated at the cathode is in the
Magnesium hydroxide being almost insoluble molten_statc (T p %4 K) It being lighter rises to
thus pre;lpitated ii filtered and f,eated to give the the surface- o-f the molten electrolyte from wh€re it
oxide. is removed from time to time by meaas of per-
a forated laddles. Magnesium thus obtained is about
Mg(OH), """'r MgO * HzO 99Vo ptrc.It is refined further by subliming at 873
K under a Dressure of 1 mm mercury.
lhe onde so oDtarneo ls converteo lnto
MsCl2 as described under I then
(a) above and 3. trlom camalllte' 2 xcl.Mgclr.6Hro. car-
electrolytic tank Ls heated to 923- 10Zi K to melt silvery white metal which soon becomes dull in air
C
the electrolyte. A stream of some inert gas such as (ri) It is a light metal with a density of
S
-----o-2
dergoeselectrolysisasrouows: ,,
"",fJtJIl'T,1il:X;"ff#,Xt?:[;""1;:';
calcium, strontium and barium. Some inrportrnt
PORCELAIN i--z -GRApH;TE chemical properties ofmagnesium are :
iJiE-":' -4-
f /.. ANooE OAction of orygen orarr Magnesium does not
react with dry air but slowly gets tarnished in moist
cHLoRtNE GAs
air due to the formation of a thin lllm o[ thc oxidc,
3!3t
-;-I_J I lJ-*coAL GAS Mgo. It burns in orygen or air with a rlazzling light.
A
2Mc+O,
CATHODE
-2MgO
of cafton diuide ond
FU'ED Qi) Action sulphur
:fiE dioxide. Because of its great affinity for orygen,
ffiELtA,rrE::=::::E-+::=.=l H%}t"'' magnesium keeps on burning even in co, or So,'
Thus whco magncsium burns in air both thc (iii) Magnesium is also used in cathodic
oxide and the nitride are formed. protection of metals and as an orygen scavenger in
(iv)Action ofhologenr. Magnesium on heating rnetallurgy.
with halogens rcadily tbrms the halides, e.9., (iv) Being a reducing agent, magnesium is
A used in the extraction of boron and silicon from
Mg + CI2 ....- MgCl, their respective oxides.
(v) Action of water Maglesium does not BrOr+3Mg-'+3MgO+2B
decompose wrter in cold but decomposes boiling SiOr+2Mg p2MSO +Si
water or steam.
It is also used in the extraction of other metals
Mg + HrO (steam) --- MgO + H2 such as Ti, Zr and Hf.
Magnesium amalgam, however, liberates H, (v) Magnesium is used in the preparation of
from cold water. Gignard rcagentr whtch are widely used in organic
synthesis.
(vi) Action of acids. Difute acids including
nitric acid react with magnesium to produce (ra) Magnesium is used for ignition of ther-
dihydrogen. mite cbarge in aluminothermy.
Mg + 2HCl MgCl + H,
.......r (ui) A suspensioa of magnesium hydroxide
knowt as milk of ma6reslc is used as an antacid for
Mg + Dil..HrSOa ....-MgSOolH, patients suffering from acidity.
Mg + 2HNO3 *Mg(NO:)z+Hu (rzii) Magnesium carbonate is one of the com-
ponents of tooth paste.
However with conc. HrSOo, SO, is produced sticTl()N-IIt
R
EE
Mg + HrSOo -->MgSOa + SO2 + 2 H2O 12.21. Compounds ol Alkaline Earth Metals
(conc.)
AR
(vii) Reaction with allql and aryl halides. Mag- Alkaline earth Eetals form many com-
C
nesium reacts with alkyl and aryl halides in dry opounds. Some of these are discussed below :
S
ether to form covalent compounds called Gignard 1211.1. Magneslum sulphat€, Epsom salt,
N
reaBenls.
IA
MgSO..7ErO.
Dryether
IIT
(ili) trlom ldeserite. The mioeral kieserite (v) Anhydrous magnesium sulphate is used as
(MgSOa.H2O) is powdered and dissolved in water. a drying agent in Organic Chemistry.
The resulting solution upon conccntration and 1221.2. Calclum oxide.., Quick llme, CaO
crystallization is the temperature range 2il5-320 K Preparatlon, Calcium oxide is called quick
gives crystals of MgSOa.7H2O. lime. It is prepared by heathg limestone in a
(iv) Iaboratory prtparation, In the rotatory kiln at 1273 K.
laboratory magnesium sulphate is prepared bydis- 1273K
solving magnesium metal or magnesium oxide or CaCO, <- CaO + COz;
magnesium carbonate with dil. H2SO4. a H -- + 179'9 kJ
Mg+ H2SOa .--........ MgSO+ + Hz It is only above 1100 Kthat CO2 escapes freely
MgO + H2SO4 """""'r MgSOa + H2O and hence a temperature of 1273 is mahtained.
The necessary conditions for obtaining a good
MgC03 +H2SO. MgSOa + CO2 + H2O
yield of quick lime are :
The resulting- solution upon concentration (i) Since the reaction is rcversible, cotbon
and cooling (275-3m K) gives crptals of dkxide should be removed as soon as il is formed in
MgSOn.T HrO. order to shift the equilibrium in the forward direc-
Properties. (i) Magnesium sulphate is a col- tion in accordance wilh Le Aadiels Principle.
ourless efforoscent (loses water of crystallization (ii) The tempeiature should not be allowed to
slowly) crystalline solid highly soluble in water. rise above 1273 K otherwise silica present as im-
Its extract formula is [Mg(HrO)5lSO..tI2O. purity in lime will combine with calcium oxide to
(ii) R
form infusible calcium silicate.
EE
Isomorphisma. MgSOn.THrO shows
Abo!,e 12?3 K
isomorphism since it exists in two crystalline forms CaO+SiO,
AR
(ni) It forms double salts with alkali metal with a m.p. of 2?i73 K.
IA
sulphates. The double salt, KrSOo.MgSO1.6H2O is (r'i) It is usually obtained itr form of hard
IIT
sold as a fertilizer un der the laame potash magnesis. lumps. When heated is oryhydrogen flame, it emits
brilliant white light called limelight,
(iv) Action of heat. When heated to 423 I( it
loses six molecules of water of crystallisation and (iii) When exposed to atmosphere, it absorbs
charges into magnesium sulphate monohydrate. moisture and carbon dioxide forming slakcd lime
The monohydrate becomes anhydrous when and calcium carbonate respectivoly.
heated to 503 K and on further strong heating, it CaO + H2O ----------- Ca(OH)z
decomposes to give MgO and SO, gas. (moisture) Galciumiilicotc)
423K CaO + CO, CaCOt (calcium caftonate)
MgSOa.T H2O MgSOr.HzO
-6H20 (iv) On adding water, it produces a hissing
-
503 K - Strong sound and a large amount of heat is evolved which
MgSOo ...-- MgO+ SO, conve s water into steam. This process is called
-HzO heating slaking of lime and the fine powder thus obtained is
called slaked lime.
Uses. Magnesium sulphate is used :
'Compounds having same crFtal stluctulc arE called lsoErotphous and the Phenomcnon is callcd lsomorPhbm.
" Non -€valuative.
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121s8 Neq, Course Cl
CaO + 2HCl """""+ CaCl, + H2O (ra) Rcactlon with chlorlne. Slaked lime
reacts with chlorine to form calcium hypochlorite,
CaO + SiO, .........- CaSiO, a con-stituent ofbleaching powder
6 CaO * PaO16"""""'r 2 Car(PO.), 2 Ca(OH)2 + 2 Cl2 """',
CaO + SO, '--""- CaSOs CaCl, + Ca(OCl), +2H2O'
(vi) Reactton ryith coke. When heated with (iv) Reaction with carbon dioxide. Whsn
coke in an electric futnace at2Tl3-3273lt it forms carbon dioxide is passed through lime water, it
calcium carbide. turns milky due to the formation of insoluble cal-
22T3-3273K cium carbonate,
CaO + 3C CaC2 + CO
Ca(OH)2 + CO2 """""'' CaCO3 I + H2O
(vii) Rcacdon wlth amnonlum salts. On heat- (Milkinets)
ing with ammonium salts, it liberates ammonia gas. on
passing excess of carbon dioxide, the
CaO + 2 NHaCI """'-+ CaCl2 + 2 NH3 + H2O precipitates of calcium carbonate dissolve to form
Uses. (i) As a constituent of mortar, it is used
soluble calcium bicarbonate and hence tlrc nilki'
ness disappeors.
on very large scale in building constructions.
a
(ri) In the preparation of cement, glass, cal- CaCO3 + CO2 + H2O '--'--- Ca(HCO:)z
(Soluhle)
cium carbide and sodium carbonate (from caustic
soda). If this clear solution of calcium hicarbonate is
(iv) It is used in the preParation of ammonia heated, the solution again turns milky due to the
and sodalime (CaO + NaOH). decomposition of calcium bicarbonate back to cal-
R
cium carbonate.
EE
(u) It is used for drying alcohols and non'
Heat
Ca(HCO)r(aa) -..."....- CaCo3(s) + Cozftl)
AR
acidic gases.
(r,i) It is used as a basic lining in furnaces. + H2Oo
C
CaCl2 + 2 NaOH ......... Ca(OH)2 * 2NaCl cor, Nor, SOr, SO, erc.
Properttes, (i) It is a white amorPhous powder
(ii) lor preparing ammonia from ammonium
salts.
sparingly soluble in water, the solubility decreasing
further with rise in temperatlutre. An aEteous sofu- (iii) in the production of mortar which i-s used
tion is known as Ettu vsbr and a susPension ol as a building material.
slaked lime in wwer is colled mllk of llme ' (iv) in white washing due to its disinfectant
(ti) Action of heat. On hcating, slaked lime properties.
loseswater odyat temperatures greater than 7fi) K (v) for softening of hard watcr.
(vi) in the manufacture of bleaching powder.
?00 K
Ca(OH), """'r CaO * Hzg. (vii) in the laboratory, as linte watar for delec-
tion of carbon dioxide,
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S-BLOCK ELEI\,'IENTS 12139
(r,iri) It is also used in making glass, in tanning (ir,) lt is alstr used in dcntistry.
industry, as a cbeap alkali for neutralising acids and
in the purifrcation of sugar and coal gas.
1221.4. Plast€r of Paris*, CaSO.. l/2 H2O Uses of lime. Calcium oide is called lime or
or (CaSO.)r,HrO. quicklime. Its main industrial uses are :
(i) It is used in steel industry to remove phos-
Plaster of Paris is calcium sulphate hemihy- phates and silicates as s/cg
dratc Casoa. 1./2 H2O.
(if) It is used to make cement by mixing it with
Prcparation.It is prepared by heatingglpsum silica, alumina or clay.
to 393. (iri) It is used in making glass.
393 K
2 CaSOo.2 HrO ............_ 2 CaSO + 1/2H2O (rv) In chlor alkali industry (includes the
production of three main chemicals : NaOH, Cl2,
Gr?6um Plastcr of Pans
+3H2O NECO3), it is used in thc lime-soda process for the
conversion of NarCO3 to NaOH and vice-versa.
The following conditions are necrssary :
(i) The temperatue should not be allowed to (r) It is used for softening water, for making
rise above 393 K because above this temperature slaked lime, Ca(OH)2 by treatment with water and
the whole of water of crystallisation is lost. The calcium carbide.
resulting anhydrous CaSOa is called dead bumt Uses of slaked lime. Calcium hydroxide is
p/arler because it loses the properties of settiog with called slaked lime. Its main industrial uses are :
water. (i) Slaked lime is used as a building material
(ii) The gypsum should not be allowed to R
in form of mortar. It is prepared by mixing slaked
EE
come in contact with carbon containing fuel other- lime with 3-4 times its weight of sand. The mixture
wise some ofit will be reduced to calcium sulphite. is made into a thick pastc with gradual addition of
AR
Propertics, (i) It is a white powder. water. The paste is called mofiar and is used in
C
'Non-e\,? luativc.
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12140
(v) Commercial limestone contai-qs iron amounts of magnesia (MgO) and iron oxide
oxide, alrmina, magnesi4 silica and sulphur, with a (FerOr) are also required for imparting suitable
CaO content of 22-56Vo. and MgO content upto colour to csment.
217o. It is used as such as a fertilizer. 12233. Manufactur€ of C€ment
Portland cement is chiefly manufactured by
the following two processes :
(i) Wet Process (ii) Dry Process.
The wet process is preferred wheo the raw
materialsi.e. lime stonc and clay arc soft, climate is
humid and the fuel is cheap. The dry process is
preferred when the raw materials are hard.
The main raw mate rials are lime slone andclqt
building stone in England those days. He, whereas the former supplies lime while the latter is
therefore, named it as portland cement. a source of silica, alumina and iron oxide. The raw
materials are hrst crushed separately in a suitable
machine. They are then mixed in the required
proportions (3 parts lime stone + one part cla,
and ground togcther finely. This grinding is done
either by the dry process or by the wet Process -
The chief components of cement are trical- In the wet process, the clay is washed with
cium silicate, 3CaO.SiO2, dicalcium silicate, water in a wash mill to removo flint and other
2CaO.SiO, and tricalcium aluminate 3CaO. R
foreign substaaces-
EE
ALO3. Out of all these, tricalcium silicate is the quantity of limesto
AR
4OVo watq.
S
The average composition of portland cement then finelypowdered and passed through3fi) mesh
IIT
'Non-c!eluatilc.
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S,BLOCK ELEMENTS 1441
RAW MATERIAL
COAL DUST
HOPPEB
DUST
CHAMBER
(iii) The lower pan of the kiln, f romwherc usal 4 CaO +AlrO, +FezO: + 4 (}O. AlrOr.FerO,
dust is blo*n in is the hottest with the temperature Tckacalcium aluminofcrdlc
ranging betwecn l7'7O -1870 K. As the chargc Due to very high temperature in this zone,
reachcs here, chemical combination takes placc
bctween lime, alumina and silica to form calcium R
about 20 - 3070 mirss melts and combines with solid
EE
mass to form grey coloured balls (ranging in size
silicates and aluminates : from a pea to that of an egg) called cement clinkers.
AR
2CaO + SiO, 2CaO.SiO, The hot clinkers are coolcd by cold air and are
C
Dicalcium silicate mixed with 7-3Vo gypstm (to slow down the
3 CaO * SiO, -
S
3 CaO * AlrO, 3 CaO.AlrO. mesh size in grinding machines. The hne powder
IIT
Tricalcium alu inate called the 'Potland cement'is sieved and packed in
bug..
2 CaO + AlrO, 2 CaO.AlO,
The flow sheet diagram ofthe entire manufac-
Dicalcium alumtnatc
turing process is given below :
Calcium silicates
Bumt at (2CaO.SiO2, 3CaO.SiO2)
17m - l8m K Addition of
powdered and mixed * Calciuim aluminates Porlland ccnlent
in a Iot tory Liln (3CaO.AlrOr, 2CaO.Al2O3) gPsum
(Cement Clinker)
Tetracalcium aluminoferrite also sets rapidly but 1223.6. Cement industrY in India
not as quickly as tricalcium aluminate. India is one of the major cement producing
12.23.5. C€ment Substitutes countries in the world. At present more than 60
units, both in prirate as well as public sectors, are
engaged in the manufacture of cement. Their com-
ceme
bined annual production of cement is about 21
creas
million tons. Of these, Associated Cement Com-
some
which is a waste Product from steel industry and
mainly consists of calcium silicate (CaSio3). This
can be added to cement to reduce its cost without
groups.
affecting the quality. In many countries, rice husk
with hith siliia content has been used to make In Haryana, there are two cement factories,
Dadi .
one at Surajpur and the othet at Charkhi
cement,
inalQn5
Q. l.sodlumflrcinthelsboratoryshouldDotbeextlnguishedbyPortritrgreater'Why?
rather
Ars. sodium reacts violentty with vatcr Producing H2 8as which also calches fire. As a result, the fire sPreads
itran Uelng extinguishid. Thereforl, HrO shou-ld not be used for cxtinguishing sodium fire. IDstead Pyrene
(CCL) should b€ used.
Q. 2. why doe-s tsble salt get wet in raitry ses.son ?
wet.
3. Alkolt Eetals
are paramagnetlc but their salts sre diaEastretic' EJrplsiD'
C
Q.
during salt formation'
ADS Alkali metals coDtain onc upaired electron (,u1) aod hence are ParamagDetis' However,
*-
S
;lecEo;s both"rcctron
IIT
iiJr":Hf,:"ffi l:'s,ti:'"
Ans (i) Duo to smaller size, Li+ is more polarising than Na+ and hcncc LiCl is more covalent than NaCl.
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S.BLOCK ELEMENTS
(ii) Due to bigger size, I- is more polarizablc than F- and hence LiI is more covalent thar LiE
(iii) Due to higher charge, Mg2 is more polarising thaD Na+ and hcocc MgCl2 more corr'alent than NaCI.
(rv) Due to pseudo inert gasconfiguratioo, Cu + is more polarising than Na+ and hence CuCl is more covalent
thaD NaCl.
Q. I l. What mokcs lithium to show properties uncorninon to the iest ofthe olkali metals ? (N.C.E.R.T)
Ans. The unusual propertics of lithium as comparcd to other alkali meta.ls is due to (i) the exc€ptionally small size
ofits atom and ion aDd (ii) hi8h polarising pow€r (charge/size ratio).
Q. 12. When ls o catton hlghly polarlslng ? Whlch olksll meaal ho6 the hl8h6t polorlsltrg power ? (N.C.E.R.I)
tut A cation is highty polarising if its chargeAize ratio is very high. Li+ ion has the highest polarising pol er among
the alkali metal ions.
Q. 13. The enthslpy offormation of hypothetlcal Cocl(s) ls theoretically fould to be - l8E kJ ool-r ond A/H'
lor Cocl2(r) ls - 795 LJ mol-1. Colculote ArE forthe disproportlorrtlo[ reactlon.
2 Cacl(s) * Caclr(s) + ca(r) (N.C.E.R.T.)
Ans. A/ H'for the above reaction = A/H'(products) A/H'(reaclanls)
-
- A./.H'(CaCl2) + d/ H'(Ca) - 2 Ar.H'(CaCD
Tberefore, the absve reac on proc€€ds better with KF thaD with NaE
It Rb sld Cs fontr supcroddcs ltr preferenc:r to oxldcs
C
ADs. K+ , Rb+ and Cs+ are large cations and superoxide (o;) is larger than cide (o2-) and perqide (ol-) ion.
IA
SiDcc a larSc 6tion stabllizcs a largc aDion, thereforc, these metals form supercidc! in prcfcrence didcs
IIT
1o
and perqide.s.
Q. 16. Vghy soludoEs oldksll mctrls ln llquld amuonlo are coaduciug parauagnctlc ond blue la colour ?
<PS.D. twt s)
Ans. Refer to Scc. 12.5.7 on B.gD 1219.
Q. 17, MsgnesluD metal bums ltr sir to givr I tbltc osh. WheD ahls ash ls trcat€d wtth tystcr, the odour olsmEonlo
can bc dct ct!d. ExplalD
AtE, Mg bums io afu to form MgO and Mg3Nz.
2ME+Oz +2M8O ; 3Mg+N2-Mg3N2
Magnesium nitride on hydrobGis with H2O gives NH3.
Mg3N2 + 6 HrO.+ 3 M8(OH)2 + 2NH3
Q. lE. Why is crlcluE prclerrcd over EodluE to rcDove lost trrces olDolsture ftoD alcohol ?
Ars. Both Na and Ca reast with water to form thcir respeciive hydrcide!. But Na readily reacts with alcohol to
form sodium ethodde but Ca reac6 only very slowly.
zqHjOH + 2Na._ 2qHjONa + H2
Therefore, Ca is prefcrred over Na !o removc the last traces of moisture ftom alcohol.
Q. f9. Whst k thc dlllcrcncc bctrrccu mllk of llDG and llEG nlter ?
Ars. A sulpension of slakcd lime, i r., Ca(OHt in water is called milk of limc bu I I clear decaoted solutioD of slaked
limc itr watcr is called limc water.
Q. 20. A plcce ol burmlDs Erg[.rtuE rlbboD coDtluue to bun lD rulphur dldde &phlr.
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12144 Pradeep's
Atr6. A piece of magDcsium ribbon contioues to bum in SO2 since it reacts to form MgO aad S.
2M8+SO2 "ul *
'*rO '
that heat cvotved keeps the magnesium ribbon burninS.
This reacrion is so much exothermic
Q.21. Alkaline earth metals olr/alrs forlr dlvalcDt catlotrs eve[ though their secoEd ionlzstloE GntbolPi6 rre
olmost dooblc thrtr their llrst lonlzotlon crthrlpi.€. Exploir.
Ars. The highcr enthatpy of lattice formation by M2+ ions more tban comPcDsat€s the tlighq second loniztion
enthalpies of metals.
orgsrlc solvcnta vtlle thosG of Bo do not. Why l]3 lt .o ?
Q. 22. Eelides oI Bc dlssolYc lt!
Atrs Halides of Be are co\raleot because of high IE of Be while those of Ba are ionic due to low IE of Ba.
Q. 23. E $laln vhy handcs ofberyllluo fuEc lr! molst alr but other al]aliDe eorth |Deiol hslld.s do nol
(PS.B. 19e2t
Ans. Beclz being a salt of a w€€k baac, Bo(OHh aod a strong acid, HCI uodcrgoe6 hydrobsis by watcr to form HCI
wbich fumes in air. BaCl2, oD the other hand, being a salt ofa strorg base, Ba(OHh and stroDg acid, HO do€s
Dot undcr8o hydrol,'sis by water to form HCI aod hence does [lot fume in air'
BeCl2 + 2H2O Be(OH)z + 2 HCI ; BaCl2 + H2O *t Ba(OHh + 2HCl
-
24. Itrhy Be and Mg do not glve charact ristic colour to the ltame vhcreoa otbcr alkDllnc earth metal6 do 8lYG.
e.
(IIIS.B. 1993)
Ans. Be and Mg hsve high ionization enthalpi€s and henc€ their \.alence electmns are not easiv excitcd.
Q. 25. Why superoxldes ot stksli Detsts sre poromagnetic while nornrsl oxldes art diamagnctlc ?
R
EE
Ar& Superoxides contain thc ion 02- which has tbe strucEre (: O : O :)- co[taining a thrcc eleclron bond, ia,
AR
it has one u[paired elec-tron and hence is paramagnctic. Normal mid€s containing the ion 02- do not have
C
lNsme thc alksu trrct&ls which form 6upGloxidcs ldben heated ln exc6s of air ? (NC.E.R.T)
Q,
ADs. K, Rb and Cs.
(NC.E.R.T)
Q. 2. Nsmc the Ectal rvhich lloats on xrtlr without ary aPPoraDt rexctlon
vlth iL
Ans. Li.
Q. 3. Nsme the chlel lsctor EspoDEible fo! the anomalous behariour of lithluh' (N.C.D.R. r)
Ans. Small size, high elecrooegatMty and high ioDization enthalPy.
Q. 4. Name the €leEcnt which ls Invarlably biYslent ord wh6e odde is soluble lE ercr6s ol Nf,OH rrtd lts
dipositivc ion bas noble 8ss core. (N.C.E.R.T.)
Ahs. Be(OHt.
C
Q. 19. Why the eleEents ofsecold rorr (lirst short period) show s number ofdilferences in properties from othcr
S
Ans. The difference in tbe properties of the first Drember of a group from thGe of the other meDbers is due [o
IA
(i) smaller size of the atom (ii) presence ofoDe inner shellof only two electrons and (ii) absence ofd-orbitals.
IIT
Q. 25. What are the raw mnterials used fo. the manulocture ofwashi[g soda by Solvay pnocess ?
Ans, NaCl, CaCO3 and NH!.
Q. 26. Why is calcium preferred ovcr
sodiuE to remove last traces ofmoisture from alcohol ?
Ans' Both Na and Ca react with water forming their respective hydroxides. In contrast, Na reacts with alcohot ro
form sodium alkodde but Ca does not-
Q. 27. Boncs contain calcium ions. What do you think would be the anion associated with them ?
Ans. PO;- ioD.
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12146 Pradcap's
Q,2t, Give one irnportont orc ofeach o[sodiuh ond pottrssiurn.
ADs. Na : NaCl and K: KCl.
Q.29. Give two ores ofmngnesium.
Ars. ClrDallite (Kcl.Mgct2-6H2O) and magnesium chloride (Mgclr.
Q. 30. Thc second ionizfftion enthalpy of calclrm is more than that of the lirst ond yet calcium forms CaCl, nnd
Ilot CaCl, Why? (NC,E,RT)
Ars. The higher cDth6lpy oflattice formation ry Ca2+ ioDs mL,e than comp€nsates the higher ionization enthalpy
of calcium.
lorEula of dolomitc rrd csrnrllltc.
Q. 31. Glve the chemlcsl
Ars. CaCO3.MgCO3 and KC1.MgC|2.6H2O.
Q, 32"lvhst ls the forEula ol SlPsum ? Whst hsppetrs wher it ls hesterl ?
Ars. CaSO..2HrO. Wben heated to 393 K it gives Plaster of Paris (CaSOa.12H2O) but at 473 K it gives dead
burnr plaster (CgSO4).
Hcat
Ars. MgSO..7 HzO; MgSOa.T H2O MgSO.. HrO - MgSO.- MgO+SO3.
C
-6H2O -tLO
-
S
Q. 37. Vvty ls lt ueccssarf to rdd gpcuur ltr the llnal 6ta8e ol prepsratlon ol ceElcDt ?
N
Ars. Gypcum is added to slo$, dowlr the process of setting of ccme[t and thus impartitrg gr€3ter strcngth to it.
IA
IIT
11. Discuss thc anomalou3 behaviour of lithiu m in its 8rouP. compare the Prop€rties of lithiu m with those
of maSnesiurD- (H.S.B. 2004 C)
C
15. when ao alkali metal dissotves in liquid aormooia, the solution acquires different colours. Explain the
reasoN for this tyPe ofcolour change. (N.C.E.R.T)
16. What happen. whcn
(i) sodium metal is dropped in water ?
35. Alkaline eartb metals form ionic salts having bivalent c€tioDs. Justify the statemenr by giving reasons
iD favour of),our answer. (lLS.B. Sanple Paper 1991)
36. In what respects does BeC'12 differ ftom the halides ofother group 2 elemeots ?
31. What is diagonal relationship ? Discuss the diagonal relationship between Be and AI. cive the points
of resemblanc€ between Be and Al. tt. & K. 1997; H.S.B. 20041
3t. Explaio the trend ofsolubility ofcarbonates, sulphates and hydroxides ofalkaline earth metals down
tbe group. (PS.B. 1992\
39, The second ionization energy ofan alkaline earth metal is higher thao its first ioDization eners'. Why
isitso? (A.I.S.B. 199i)
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S-BLOCK ELEMENTS 12149
40. Why do alkalinc earth metals not (rccur in the ftee state ? Name some important minerals of
magnesrum.
41. Holr does magDesium occur in nature ? Hor is lhe magnesium metal obtaincd by the electrol,6is
method ?
42, Why alkaline earth metals cannol. be obtained by reduction oftheir dides with carbon ?
43. Give reasons for thc following ?
Beryllium qhibits some similarities with aluminium. Poi[t out tbree such propertics.
C
(N.C.E.R.T')
Like lithium in Group l,
beryllium shows aDomalous behaviour in Group 2. Yy'rite three such
S
N
(i) C€ + Hzo
0i) BeOH + NaOII
('lr) C€(oHh + Cl2
(iv) BaO2 + H2SOa. (N.C.E.R.T.)
Cootrast the action ofheat on the following and explaio your aDswer:
(i) Na2CO3 and CaCo3
(i) quicklime
(i,) gypsum
(iii) calcium carbide
(iv) magnesium sulphate.
5E. Describe the importance of the following :
(i) limestone
(ii) cemeDt
Paris.
(iii) Plaster of (N.C.ER-TI
ste I.2.52.59. Listthe raw materials required for the manufacture ofPortland c€mcnt ? Whatisthe role of$PsuDl
in it (N'C'E'R'T"'
60. Whar is the effecr of hear on the followiDg compounds ? (Write equatioDs for the reactions).
(i) Calciunr carbonate
(ii) Magnesium chloride hexahydrate ?
(,,t) G}?sum
(iv) Magnesium sulphate heptahydrate.
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L CARRYING 5 or rnor6 MARKS
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Sec. 12,1. 1. Discuss the position of lithium in the Periodic table. How does it differ from other members of the
C
to 12.20. famity ? Ib what other elemelts iD the Periodic table does it resemble t Justiry your answer with
oramples. @.1.5.8. 1990 C)
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suitable
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2, Give general characteristics of alkali metals. Discuss thc anomalous bebaviour of lithium. Mention
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3. List some imponanc€ ores of lithium. Discuss the various difficulties encountered in the extraction
ofalkali metals. Describe briefly the extraction of lithium ftom a silicate ore.
4. How is sodium obtained ry the Down's process ? Write equations for the reactiom involved. Why
sodium cannot be obtained L'y electrolysis of aD aqueous soluiion of sodium chloride ?
Describe iD detail manufacture of sodium carbomte by the solvay process. State the PriDciPles
iovolved in rhis proc€ss . (N.C.E.R.T'
Why is it thatJ-block elements Dever occur free io nature I What are thgir usual modcs of occu rreDc€
andhow are they generally prePared ? (N.C.E-R.I)
1 write three general characteristics of the elements ofJ.block of the Periodic table which disrinSuish
them ftom the elemcnis of the other blocks. <N.C.E.R.T)
Crmpare the solubility and thermal stability of the following mmPounds of the alkali metals with
those of the alkaline earth metals.
(4) nitrates (c) carbonates (c) sulPhates (N.C.E.R.T\
9. MeDtion the geDeral treDds in Group 1 and Group 2 with increasing atomic number with respect to
(i) deNity (ri) melting point (i.i) atomic size (iv) ionization erthalPy. (N.C.E.R.")
How do the following proPeriies change on moving froD Group I to Group 2 in the Periodic table ?
(i) Atomic size
(ii) Ionization eothalPy
(iii) Density
(iv) Meldng points. (N.C.E.R.T)
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S.BLOCK ELEMENTS 12!51
11' ComParc and contrafi the cicmistry of Group 1 mctals with thcc of Group 2 mctab Mth respcct to
(r) natur€ ofcddcr
(ir) lolubility and thcrmal stability of carbonatB
(sr) polarizing pof,.cr of cations
(rv) reactiviry 8nd r€dudtrg pcnEr. (N,C,E-R"T)
12, Tbc chcmfutry of bcrylliuE ir mt esseoually ionic. Justlry tbc lurtcEcnt brr meki[g a rcfsrsBcc to the
nsturc of cidc, d oride, fluodde of bcryllium. W,CA.R.D .
13. Give any.thrce Point! ofsimilarity between beryllium and sluminium and mo points ofdbslmilarity. '
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Sodium Peroxide
1.
Manufacture. It is manufacturcd by heating sodium metal oD aluminium trals in CO2 free air'
2 Na + 02 (air) -.... Naroz
peroxide is due to
Properties. (i) Pure NEO2 is colourless. The faiDt yello\r'colour of the ordinary sodium
R
the presence of a small amount of sodium suPeroxide (Nao2) as an imPurity' The
ycllow colour' however'
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disappears when it comes in contact with moist air due to the formation of NaOH and NqCO3 Thus'
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4NaO2 + 2Co2
-2NECo:+3oz
zNa2oz + zHzo .- 4 NaOH + 02
C
2 NaoH +
N
a
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S.BLOCK ELEMENTS 12153
(ii) ILs aqueous solution contains a high concentratioD of oH- ions and thus precipiEtes insoluble metal
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hydroxrdes ftom their aqueous solutioos contaiDing these catioos :
;
Fcrric hydroxidc
C
'n'u:H#i"'."
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The hydroxides ofAl, Zn, Pb and SD being ampboteric dissolve in excess of NaOH giviDg cl€ar solutions.
Za(oHh + 2oH- [Zn(oHL]2-
- Zncatc ion
or Zn + zOH- + 2H7O [Z1(OH)4]2- + H2
-
AI(OH)3 +3oH- ..- [AI(OH)6]3-
Aluminatc ion
or 2Al +6OH- +6H2O 2 [Aj(OH)6P- +3Hz
These metals also dissoke in NaOH liberatiog H2 gas.
-
U:o NaOH is widely used ir (a) soap, paper, textitc afld petroleum industry (b) thc preparatioo of pure
fats and oils and artificialsilk.
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12154
(T,IAIJTISJ SI2ECIAL
' Hotd ls snhydrous mognrsluttr chlorldc pre' Q. 3, It ls necessry to add S4lsum ln the llnal Etsgc6
psred ftlm ms8tresium chloride hQxshydrote ? ofpreParotlon ofcemenl B(ptstn why ?
Ans. Cypsum (CaSO12[I2O) is added in thc Enalstages
Ans Adlrdrous MgCl2 caDrot be PrePared by simPly
oi preparation ofcement since when Hzo is added
he€ting MgCl2 . 6 H2O bccausc it gets
to cement it slo\ s do\r,n tbe PrGess of setting of
hvdrotvsed bv irs otrn u,ater of cr)Etallization' cemeot so that it Sets sufficie[tly hardened thcreby
rrigCh. o ILO- MgO + 2 HCI + 5 HzO
imparting Sreater stength to it.
mchlorid€ is hcatcd Q. I . Whqt is fly 8sh ?
650 K it clt€d!8 the Ans. It is a waste Product from iron industry and has
the tDdrated ma8' proPerties similar to that of cement. It mainty
r ofcrystallizatbn to consists calcium silicate (casio3).
form anh)dr$s magnesium chlffi'e Give brtefly the lsolatlon of mogneslum ffom
Q.5
-'
Hcl -'
ca6
MgCh+6H2O seo wster lry the Dow Proces& Give cquotions for
MgClz.6H2O
- lneolved. (I.I.T 1993)
630 K the steps
(). 2. Account for thc followltr8 : AJls. See pages 1230.
(i) Be(OE)2 ls lnsotuble but Ba(oH)2 ls fairly Q 6. MgrN, *h"o reacted with wster gives ofl NH3
soluble ln w.ter. butHCl ls trot obtrlned ftom M8Cl2 oD rcactlon
(ii) Be(OH)2 is smPhoterlc whlle Mg(OH)2 ts
ivith woter at rooE temP.rature. (l'I'T' 199t
hasic. R
Ans. Mg3N2 is a salt of a strong base, M8(OH)2 and a
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Ans
weak acid (NH3) aod heDce gets hydrolyscd to
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than that of M8, the M-OH bo[d can break lcss does noi undergo hydroDsis to give HCI'
N
easily iD Be{OH)2 than in M8(OHL. In other Q 7 The cq'stalline salts of all@line e,rth mctsls cotr'
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wot&, Be (o Hh ocls ot a weak boY even weaker taln more rflater of crystalllsstion than the cor'
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CaCO3
(v)2NH1CI+Ca(OHt-
+
2NH3+2HzO+ G0z
H^O (E)
Thtts, A = Ca (OH)2,
1A R B = NH iHCO3,
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C=NarCOj,
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D - NHpt
C
and E = CaCtz.
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CHOTCE ItfrsTtoMs
^,tllLTlPLE CPMT, BHU
1. The raw matcrials used in the maaufacture of 4. Whicb of the following is not prese[t in cement ?
sodium csrboMte by Solva /s proccss are :
(c) Gypsum (6) clay
(a) Ammonia and carbon diffide
(c) Alumim (d) Alum.
(D) Sodium chloride and carbon diqide 5. Which of the fo[orring bas the lourcst mctting
(c) Sodium chloride, limestone and carboD dimjde point?
(d) Sodium chloride, limcslotre and ammonia. (a) Ucl (r) Nact
Glauber's salt is (c) KCI (d) Rbct.
(a)FeSOa.7H2O (6) MgSO..7H.O 6. Whici of the folloring alkaline €arrh metal sul_
(c) NECo,.1oH2O (d) NqSO..t0rLO. phates is least soluble in water ?
(a) BaSOa (D) Mgsoa
Plaster of Paris is
(c) SrSOo (d) CaSO1.
(a)(crsoah.H2o (D) c8so1.2Il2o
7. The basic character of thc oddes, MgO, SrO, K2O,
(c)Casoa.tl2o (d)C8sO1.
NiO and Cs2O increases in the order :
(a) M8o > sro > Iqo > NIO > Gzo (c) excitaiio[ of frec electrons
(d) existence of body ccntred cubic lallice'
(r) Cqo < K2O < MSO < SrO < Nio tI I. l: 1939)
(c) Nio < MgO < Sro < IqO < CqO
< MBO < Sro < cszo' 16. GyDsum on heaiing to 390 K gives
(d)Y.zo.Nio (.t'caso1.2H2o (6) caso4
& Which of thc following are arranged in hcreasiDg (c)CaSOa.l /zHzO (d) SO3 aod CaO'
order of solubilities ?
\C ItM'l: 1t)9i\
(o) CaCO3 < KHCo3 < NaHCO3
17. The by-product of Solv
(6) NaHCo3 < KHCOT < CsCoJ (d) Carboo dioxide
(c) KHCO3 < N8HCo3 < CaCO3 (c) Calcium chloride
(d) caco3 < NaHcO3 < KHco3 i,
9. The thermal stability of atkaline csrth metal car- 1E. Thedrying agentwhicb absorbscarboo dioxide and
booates decrcascs in tho order ;
reacts violeotly with water is
(4) BacO3 > srCO3 > caco3 > MgCO3 (4) Sodium carbonate (b) Almhol
(c) Conc. H2SO1 (d) Calci'rm oxide
(D) BaCO3 > S[CO3 > MgCO3 > CaCO3
t B. H. t',. 1991\
ldeDtiry
(a) sodium atoms (D) sodium hydride orderof theirlncreasingthermalstabilities
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(l.l.T. 1981) Iqco3 0), Msco3 (Il)' caco3 0ll)' Beco3 0v)
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lithium because, it i"j tv. tt. r. ttt (d)ll < w< III < I
t I.l.T. 1996\
(a) has higher atomic weight
(lr) is a metal 21. Among Ko2, AlOt , Bao2 and Nor+, unpaired
clectron is Prescflt in
Bao,
(a) Nor+ and (D) Ko2 and Alot
(c) KOz oDlY (d) BaOz only'
of t L I.',l. lt)97t
(r) Al3 t 1a; la+ 22. Property ofalkalille earth metals lhat increaseswith
(t.t.r' tesl) their atomic Dumber is
(c) Be2+ (4 Mf+
(a) ionization ener$/
14. The comPound insoluble in acetic acid is
(b) solubility of their hydroxides
(4) calcium oxide (D) calcium carboDate
(c) solubility of their sulPhates
(c) catcium oxalate (d) *1"luo, (I I T le97t
Y;?Iil;,, (,J) electronegativity
23. C.alcium is obtaiDed bY the
15. The metalliclustrc cxhibited by sodium isexPlained
by (d) Roasting of limcstonc
(a) diftusioD of sodium ions (6) Elect