I'

This chapter is designecl to help with the internal assessment of pracrical rrork.
It will also be useful in ansrvering question in Units 1 and 2 that are.based, on
precticai $,ork for exaniple, enthalpl'experiments and tirrations.
-

Tests
Tests for gases
Tlie ttsts gsed to idr:ntifl'ilte cotrmott laboratorl'gases have to be learnt- It is
a)so impcrrtant to [e ab]e to drau, conclusiolts trcm the iclcndfication of these
gases. ior exanrple. if diiute sulfurjc acid is added to a solic and a gas is produced
that iurns limeuarer nrilki', the conclirsions are rhat:
I the gas is carbon dioxide
r the'.lnkno$,n solid is a carbonate or a hvdlogencarbo:ate

I I-i.drogr-=n

Test: ignrte the gas

0bservation: bur:,s with a squeaky pop

ll1'tlrcgen is protluced bi,:

r tltt: reactir;n l'retr,';ten an ircid iltrd a rcactive n:etal . .

t lhe reaction bctir'een an aicohol ind sodiurn

r ihe rei,c.tion beilr,een water and eithrr a grolrp 1 meiei. or calcium' straniitlm
or tarium

Cx-r'gen
Test: ptace a gtowrng wooden sptint in the gas
0bservatiotr: sptint catches fire

Oxygen is produced by:

I headng a group I nitrate (apart from LiNO1,)
r headng other nitrates, but NO2 is also present
r the catalltic decomposition oi hydrogen peroxide, H2O2
Carbon dior:iJe
TesE pass gas into limewater
0bservation: [imewater goes ctoudy/milky

Carbon dioxide is produced bY;

r .the reaction between anacid arrd a carbonate or hydrogencarbonate
r heating a carbonate (apart from sodium, Potassium or barium carbonates)
r heating a group t hydmgencarbonatt
 iil---...ptacedamilre4[tmuspaperint}regas...i''.
Observation: [itmus Papergo€s btue

Ammonia is'Produced bY:

anrl aluninium polider to a nirrate

, r'rdding aqxgous
'"di;fid;de
i.ii"-"
-
Ninogen dioride
observe cotour

0bservation: gas is brown

bY:
Nitrogen dioxide is Produced
i i.",i.g a Sroup 2 nitrate or lithium nirate

Chlorine
gas
iest: ptace damp litmus paperin the

0bservation: [itmus is rapidty bteached

Chlorine is Produced bY:

r electrolysis of a solution ofa chloride . . chlorate0) ions
, nya..r,toric acid to a solutioncontaining
"'a-il;;;.
Hydrogen chloride
Te 1: ptacedampbtuetitmuspaperlnthegas
paper red
Oir.rrrtion, 'tt'*y fumt' that turn damp litmus
ptr,. th;';;;pt' t'o* a bottte of concentrated ammonia in tne
Test 2:
gas

Observation: ihitt smoke (ammonium chtoride) is formed

I{ydror.n chloride is Produced bY:

conctnuattd sulfuricacid and a chloride i
r the reaction between ' '
penlachloride and either an alcohol or a
r the reaction Utt*t"n ff'osphorus

Sulfurdioxide sotution in the

Test: ptace fitter paper soaked in potassium dichromate(u)
gas
'0bservation: cotour changes from orange to green

Sulfur dioxide is Producetr bY:

;-;;;;i"s ,n,'id with a s6lid sulfite
r buming sulfur
acid
i reducing concentrated sulfuric

formulae of the ammonium ion'

NHa" and common potyatomic
@You mustknowthe S04e-'suffite'
hyrdrogencartonab' Ht'ca-' sulfate'
cat"tit'
anions. such as
. i*r;-;;ior,.
'O'*'
NOi and chtorate(I)' cto-' : I ::

sobdsarethose of groul
l metab'
@Ihe onty hyarcgencarbonatc thatexi*as t'r"-1;,

Chemiiiif' laborotory'skills l'

316 Unr'r 1:
 ir .i;,:l;?. '. :ji.:, . !.;. .
=i;:-r.;i'-:
:
-.--/t*|--- -.i.L:1 :-.:. r: I r,. ), : t

-.t -,-
-\ _ ...,rir::i-2;.

Flame tests
To carry out a flame
test, a cleon platinum or nichr
conentrated. hydrochlo.L
the hotest pan ofa Bunsen
a.l4 then inro,h" r;;':;n;"':ffi: Hffi il:;
flarne.
The concentrated hydrochroric
acid conver* some of the unkrown
chloride' chlorides are more sorid into a
vorarire ,irr, r"lts, so some of the unknown
when heated in tn""*.r
goes into the gas phase
t"
r,ot n",n.. ilo.,;;;*"I*o
i Tgl* :nergy
lever by the heat. I*hen rar, ir.t to the ground srate and
emis light of a corour specific to the metar pr.ru*- in che cornpound.
obtained in flame rcsB are given -' Tfie corours -l'--'-*
in Table ;i.;.
Fhme olorr lon pr€sent in sotid loile 17.1
frimson Flanr.,colous
Li-
Yellow Na-
I-ilac K+

YeUou+ed Ca?*
Red
5r2t
Pate green
Ba2"

@ ihe ftame testis the onlytestfora group 1 metat in

a compound.
@ Ftame tests cannot be
used. on mixtures containing two oftheseions
coour produced by one becase the
of the ions wf tt mask ttre corrr" pr.r*.0 bythe othermetar
loF.

Precipitation reactions
Ir is important ro krow which
ionic compounds are solubre in
are insoluble.
water and which

Soluble ionic compounds

include:
r all group I salts
r all ammtnium saks
x all nirrates
r all chlorides, apart ftornsih.erc,oride
and. read(rD chroride. (The
of bromides and iodides is sorubiliry
similar to ,f,rioi.f,fo.iao
r all sulfares' apan from barium I
surfatq ,oonJ,,i sulfate and
Caicium
lead(u) ruifrte.
sulfate and silver sulfate
,figt dfl;uUf
Insofuble ionic compounds includer
"* ".
r a'll carbonates' apart from group
l carbonates and ammonium carboaate
r alt hydroxides, aparr
.
arnmonium hydroxide. Calcium t {i"r,*d Mr;;;;r, barium hydroride and
1
soluble.
;;;; hydroxides are slightty

The resulre of some prccipimtion

rcactious are shown in Table f1.2.
 lattu tLZ
-t
I
soruttuns contaifttts stese !q:te ,!ttg frui@ion
Bakand 5012: (suffieionscoutd befrom
. t{hite precipitate of barium sulfate ' tetr,rtiws

sotutions of group 1 sutfate,

ammonium ' r 0n adding ditute hy'droclrtoric acid, the
piecipitate remains
sulfate or from sutfuric acid)

Ba2'and 5012-
r $ihite precipitate ofbarium sutfite
o 0n adding dilute hydrochtoric acid, the
precipitate dissotves with no fizzing

Ag; and Cf- (silvericns are

normatty frorn a r ChaLky-white precipitate of sitver chloride
sotution of sitver nitrate) . ' r Pacipitap dissor-ves in diiute aqueous
ari-ronia

Ag" and Br-

r Cream precipitaie of sitver bromide
o Precpitate is insotubte in ditute ammonia.
bui sofuble in concentrated ammonia

Ag* and I- . Pale yettow precipitate of sitver iodide

r Piecipitate isinsotubte in both ditute and
concentrated ammonia

C032-and 3ny cation, otherthan a group 1 r v"hite precipitate oftheinsotuble metal

*.i.t or rr*orium (orbonate ions cculd be caibonate
from sotudons ofgroup 1
carbonates or r 0n adding acid, the precipitate fizzes as it
,m*ouiun carbooate) gives off carbon dioxide and disappears

re-actions will alrvays be of the form:

The ionic equations lor these Precipimiion

For example, the ionic equation for the

formation of barium sulfate by mixing
is:
,oturtont Lf uarium chloride and potassiun sulfate
Ba2.(aq) + S0az-(aq) -+ BaS0a(s)

Tests for anions

Sulfate
dilute hydrochlorieacidjoltowed @*eaitute
To a-solufion of rhe suspected sulfate, add hydrodrtoric acid
which remains when excess
it ***t barium chloride; a white precipitate,
of sulfare ions' canteadded before
toti. acid is added, prol'es the presence
iiaro.t thebryium chtoride.
Thefwmation of a
Sulfite
If it is a sulfite' zulfur pre@ate proves
io ri" tutp..ted sulfite, add dilute sulfuric acid and warm'
a piece of filter thepenceof
it*ia. gas will be given off' This is tested for bygas'placing
A colour ch-anSe-from sulfabions.
,rn.r *if"a in potassium dichromate(vr)
in the
in the original
il;;" ; ,*"n on th. paper confirms the presence of sulfite ions

'solid.

an unknown solid or a solution of the

This test can be carried out on either
unknown.

Caftonate
;;dil" sulfuric acid ro the suspected clblnate in solid form' If it is a
off' This is tested forby passing the gqs
;;";;;;, carqon dioxidewill be.girren
into limewater, which goes milkY'

318 lJnft 3: Chenist'y lahqo$4y lkills.l

.r :i
Alrernatively, heat the solid. Carbonates,
other than socliurn, potassiuru and
barium carbonare, give off carbon clioxide.

Hydrogencarbonate
To distinguish beh,veen a group 1 carbonate and a hydrogencarbonare:
e add some of the unknown sorid ro armosr
boiling ivatei. I{ydrogencarbonares
decompose with the production of carbon
dioxide fizzingo"..rrr. carbon
dioxide can be tested for by passing it into limewarei; -
which"goes milk1,.
or
a add a solution of the unknown to a sorutjon
of carciurn chloride. Hydrogen-
carbonates do not give a precipitate because
calcium hydrogencarbonare is
soluble; carbonates give a white precipirate of
calcium carbonate.
or
E test a solution wirh pH paper. carbonares
have a high (arkarine) pr{ w}rereas
hydrogencarbonates are armost neutrar.
on warnring, if the solution is a
hydrogencarbonate, the pH rises rapid\, as the hydrogencarb6nat":
-'r -'-o-"-!
decomposes ro give a carbonate and
carbln jioxide.
t.liloricle
lb a solutiolt of tlte suspectecl cirloride,
add dilure rritlir: acid uniil rl.re s,r.)I:rion
,r' isjust ar:idic (test with litmus p.;.rJ.
white precipitate, which dissol'e.s when
ih.;,lJo ,,,,., nitrate solution. L chatkr..
excess dilute arrruronia is a.rled,
1r.o.,*,,
the prcsence of cliloriile ions in the original
solution.
Brorrritle
'lb a solutiott of the
suspected bromide, add dilute nitric acitl unril
tlre solution
is just acidic (test with litmus paper).
Then, add siivei. nitrate s'iutiorr. A cr-eani
precipitate, which is insoluble in dilute
ammonia but dissolves in coni:entrared
amnronia, proves the pl-esencc of bromicle
ions in the original solution.
fut alternative test
is to add chlorine \,iater to a solution
of the unknorvn. Bromicie
ions are oxklised to bromine, which turns
the colourlcss solution lrro*,.,.
']odide
The resrrltr,,outd he
To a solution of the suspectecl iodide, add
dihrte nitric acid until the solurion is the same if broml'ne
just acidic (tesr with litmus paper).
Then, ,il;.;;i;;:;i;;on. o ,u,* watel'had been
yellow preciilitate, which remains nrhen "d;
conccntrated amrnonia i.s addecl, proves added. tlromine is a
the presencc of iodicie ioniinthe orrginal
solurion. stronger oxidising
A, alternieti,e test is to add chrorine wate r
to a solution of the unknon n and then
agentthan ioCine
add a few drops of an organic sor'ent such and thercfore
hexane. Iodide ions are oxidiseci
as
to iodine, so the colourless hexane raye. cxidise.c iodide
tur,s violet. The presence of iodine from
the oxidation of ioclide ions'can also
be deicted by adding r,ur,,rr, ,rhi.h t.,rn,
{ ions to iodine.

blue-black.
 e&t" aoing this t?st
{ that
alloy and sodium you need to show
aluminium powder or-Derrarda's
Ilff tr*"*,oiid, "dd are reduced to ammonia' which thecomPound is notan
and then warm' Nitrate ions
bydroxide solution amnronium salt' as
canbe.detecteauytt,"gus;,ouedturningdampredlitrnuspaperblue. ammonium salts give I
i
ammonia when heated
k
' ontyconctusive if ammoniurn
ions have been shown to be
absent' They
with atkati.
r
t
I
@This testis presentin this tesl
by reacting with the atkati
Xr;;rrd;;"ammonia
,brown-ring, rest. IIix together solutions of the unknown
An aiternative is the sulfuric acid dolvn
carefull-l' Pour some concentrated
and iron(tt) sulfure' Then acid and
,''irrg forffi where the concentrated
rhe side of the test ,br.';;r;;
aqrleous laYers meet'

Tests for cations

Ammonium hydroxide'
solution r'vith aqueous sodium
lVarm the unknown solid or bi detected by placing damp
ofi"n*o'iugas' which can
Ammonium salts give
paper biue'
ilil;; prp., in the gas' Ammonia turns the

GrouP l and grouP 2 cations (pages 212-13 and 317)'

cation"" atttt'ed by the fiame test
Group I and group 2

coiourless in solution and

do not colour a flame' but are
i,:lagnesium compounds caibonate
ot'*"gnt'i'* carbonate r't'hen ammonium
eive a rthite precipitate
Eoltrtion is added'

p-block and d-block cations is tested at A2'

of p-block and d-block elenents
The detection oi the ions
groups
Tests for organic functional
I'est tbr a GC bond containing a C=C bond
the test compound' Compounds
Add bramine water Io
water from broln to colourless'
t"' if" t'oti""
iunsatutated compounds)
Test tbr a C-OH grouP
to the anh-t-drors compotlrrd' If the
Add solid phosphorus pentachioride and alcohois)' steamy fumes
(carboxyUc acids
comrround con,.in' u c-oJgtup bv putting damp
il,fi;;;:;;iro,iat t"lr-ut p'oautta' This can. be detected
Hvdrosen chloride rurns the
l'n.us red'
;i,,J;;';;ii" s,,'

gives a resutt
- @ Oo not state that this is a test for atcohols'
If a com Pcund
itis
Posittve
a carbo;<ylic aciC cr an
to determirre vrhether
for a C-0H qroup, yo' tl'en have iiiiie ethanol is
tetween the two' aad sonre ofthe
testcompound to sodium A
aLcohol- To difinguish giwn to
sometimes added
en acidwill produce fizins as carbon dioxideis
;il;;;;;;rt,.it'r"tlon' hdP dissotve the
oit nitt' ,n at ohot there is nr' reaction' habgenoaltane and
-{

brinq itinto contact with

TestforaGhalosenFoup for several minutes' being
. .--L- ( thchydrofieioas'
lvittr aqueous sodium hydroxide
Warm the unknown to
organic compourd' Allow the solution
boil off aioiatile
."*fui ;";ro
skills I
320 ,Jnit 3:Chenisuylatsorototy
 i:.{i',t-f T?::!}jr ::,j:: j,.,:-1 -:: ;,..:_:.; ;1. :

*:+ii{:j74+.*:.,l'' x
*-':.>iitJ.ii:+rt -. - :,r_.i:.-.+

@o[ Add nitric acid until the sorutioo

is just acidic to liruus. Then,add
nirate solution. si]ver { fheorgafthalogen
i
chlorides give a white precipitate " compoundis
i

t-
' 9tryit
indilute amrnonia.
of silver chloride, which is soluble laf,rotped byttre
sodium hydroxile
I
I
r oryanic bromides give a-aeam
precipirate of silver bromidg
I which is insoluble to gire halide'funs
in dilute ammonia but dissolves
in.*.un*r.l-r*roonir. in sobtion, whictr
r organic iodides give a pale y.,o*
p.."ipir"ie of silver iodide, which is then reactwith the
insoluble in both dilute and
.oo..norla silvrr ions to furn a
Alkanes
"irr_i. precipitate.

There is no test for an arkane' Ifa, the above tests

are negative, the unknown
(limited tO organic substances @Rememberthat
corcred .t eS; irp.oUably an
alkane.. an organic unknown
may contain two

Organic techniques frrnctionat groups. .

expected toknowtechoiques used in

9t:r:"
able to draw diagrams
organic preparations. you must be
ofthe necessary apparatus and knowwhen
to use each
method.

Heating under reflux

organic substances
are voratile and the rates of many
organic reactions are slorry.
Heatingis used to speed up reacions,
but if this is done in an open vessel,
as a beaker, the organic readantand suih
the product may boil off. To prevent
happening' a refrux condenser is this
ued. ,'r. organic vapours that boil
reaction mixture is heated are condensed
offas the
ara iow uact into the reacdon vesser.
tu most organic substances are flammable,
it i, ,rf"rio r,.l;.;#;H,
an electric heater or a water bath rather than a
Bunsen burner.
F$urc 17.1 Apporatls
The essential points ofthe apparatus (Figure 17.I) lwhating under
are: $ux
r a round-bottomed flask
r condenser with the water entering
1r..ff* at
the bottom and leaving at the top
r the top of the reflux condenser being open
r the flask being heared using an ule.t icieuter, lYaterftt
<L-
a water or oil bath or a sand tray

Reactions where heating under reflux

is
necessary include:
r oxidising a primary alcohol to a carboxylic acid
r oxidising a secondary alcohol to a ketone
r converting a halogenoalkane to an alcohol Round.0ottomed
I converting an alcohol to a bmmoalkane
bv
flask

reacting it wirh potassium bromide and SO%

sulftric acid
Heat under reflux
 i' l
waLiebigcondensetcorrecB'*'t:Y'l"T:':;;'
with water flowin g iround

ffi ffi#:H:.:fi H ['."#;; ;;;"*' ; a si n ste nit - there

m ust u
,
fl
bi a join between them'

reactions do not go
to comple::1":'.tffi:;[
Most organ'c ispresent tna ffi:t[:|!Ht:::-,
#;;;;rt that the desired prodqct species' sttch
caq ot from non'voladle inorganic
so they
,re voiatile, 'lpttt*a
distillarion'
,;;;;t alkatis, bY
boiling temperatures ::'::-,^:"1'
th cifference in the to separate then
ui"d
'ff::iil;:Iff ;ilT|-il[:1il:.#"*i;''"'o"

:'::**ffi :,":il:*:#ifr ifi :-"4:1:I"8.'h:T',I.'l*-*^.,,,. tn" uuru o?*nitr., must

be posirioned
r *nfl"'lit"l"*"*
' a srill-head outlet of the stilt'head
lr=i *,* the "tt"u
the bonom and lea"ing
at the top
ra conder'set *i* tr't'iJi"t';*i; ": open to the airioined
;'-t' u'-u utut"'' o' 'n-ua'ptot
E an opetl:ec"iuillsn"*[
flask tray
to a :
- ^- eiectric heatcr' a
^16^rr;..hparcr. I lrater oroil bath or sand
heated using an
, ,iJtrr'*oting o\:er at + 2"C of the
heared anct the vapour'that comes ts
'l'he nri.stute is carefully
of the parricular subsrance
o*ul
("1.r#e.J;; ''it*
lioiiing lerr'Perattlre
. and collectei'
Fqwe 77.2 APParoitis
"n.l*s"d
lrrsimPte di*illatiat
Tiprmometei'

Sti[, nead
Water out
Ii .t
d/t Qilake sure '.hat

*<<=/ tlre toP oi the stiti-

head is ctosed and
that the Liebig
cordensar is irawn
wBh a waterjacke't'
[.ound-botromed
tlask @You musiceabte
todnwthehto
tyPes of aPPa-atus
trstlation wittr additlcF 0i re?ct'ant strown in Figtres
]'illand17'2

Safety issues
;";;,,*'*::':#,,:Tff
aparticulr exPerirnent' s
ffl fi :T:T}'fil*Xti,:.ilf:'H
]
a

the followng: I
I
I
t
t
t
loborutory skills I I
322 tj'ift 3::hemisvy I
 i.:i:i.::i:.i:i::?ri,:.rr--..::.; :i. ::-:-.,
?'i;r:.:li;it;i.;t*;..:;..-' j;
.
:.::i'r,;,i.11:.1:)/.+ ,r,
-.

r Distillation and heatins rmder

reflux'ust be carried out in
if the vapour of one of rhe
reacunts
a fume orpboard { ntapplies
is harmftr, poisonous (mxic) , tofialogens,
or initant. ";;;;;
r If a mixn'e is being heaed
under rdrux or disti,ed, theie
ftdrogen halides,
must be some outret halogenoaltaqes
to the air. If there is
and amrnonia.
** o,t*",,";;,;#li:'ffiH::li
:

r_ Gloves musr be worn when corr"iir.-;irir,*.*

;[.T $:Jlr]ffi ,",1*r'
are used. such substances
must always be handled with
care. --=----.,1 { ilris appties to
r The flask shourd never be
heated with a naked Bunsen
concentrated acids
flame- This is because and all<atis.
aimost all organic substances
are flammabrelna ir,n"
were [o spill over or tle flask fiquid being heated
to crack, a fire would result

@It is assumed that raboratory .oats and eye protection

are always worn wheri
carrying out practicat wo*. Therefore,
credit-it not gir;n forstating
a specific safety precaution. : either ofthese as

Yield
@rou mustbe
yieids are
Iess than 10006because of: ableto calculate
r competing reactions theoreticatyieid and
r handling Iosses during purification percertageyietd
(pages 68 and
280-81).
Enthalpy change measurements
Enthalpy of combustion
The method for determining
the entharpy of combusrion
ethanol, is described r of a liquid, such as
wavs to increase the accuracv
of the
experiment,"rri" ,i.'[,?iirti*l^"
I The copper calorimeter strouta
U. first weighed empty and then
containing water. A,ternad'ely, when
water could u. aaa"a ,o irr".ur;ri..i*
a pipette, not a measuring.yiina"r. ,rr",
ff the volume of water is measured,
mass is calculated using the the
density of *"te., which is 1 g
r cm_t.
A screen should be ptaced amund
,t. *ro.i*ur"r;; ;;r:;;
the transfer of
heat from the hot combusdon
r To ensure an even temperature
gases ro ii. U".f,", of *r,"..
be sdrred continually.
throughout, ,h.;;;;.;;e calorimetermusr
r The remperature of the water
shourd be measured for severar
Iighring the tuel and forseveral minutes before
r The temperarure-rime measr.*..ro
minures ,f".or"t;;;;;il;#.r;;..
theoreticar temperarure rise
* *"iil
pto. grrph from which the
"
is estimatea uy erruporarion.
error caused by heat loss from Tfus reduces the
the beaker o the surroundings.
r The burner and its contenr shourd u. *eished
b"fore and immediatery after
the experiment, using a balance
,h", ;;";-;;*r_cy
of 0.01 g or better.
Tte calculatiou is carried ant
in three steps.
ftp r: heat produced by the
ombustion of the firel m x c x
= Af
 buml lhe'
'
.-9. 1'
*'Jj:[:[ffi s of rater in tJre beaker' noi the
ff;;; .c-i-'",i.,*
mass of fuet
t'* p'oau"o
"r'ni
isSoutes, not htojoutes'

Att combustions are

mas before - mas after
fu.I -
exothermic, so the
Step 2: amountof iuel burnt= ;"ffir""f vatue cf AH,is

lHc= -;;6;f*lb"*,
heat Produced { negative.

Step 3: enthalpyof combustion'

and enthalPies of solution

Dis placement reactions
rhe enrhalpy of
and experiments to determine
in both disPlacement reacdons
a liquid th" t.mp.rature change is measured'
*d
,ofu.io", a solid is added to
of copper
AH' of reactions'.such as the displacement
The method for determining on page 84'
by a more reactive metal' is described
trom copper suliate solutio"n of a solid'
is used t0 fina the enthalpv
of solution
;;;;J;",hod
are not
are necessary because the reactions
Temperature*tirne graphs
instanianeous

Errors can be red'-rced bY:

speeds up the rate of reaction'
r usilg porvdered sclid rather tnan lumps' This
,o ,i*i" is lcss tirne t-or coolirg'
encugh metal is taken'to ensure
. ;.;;;; iirat, for displa':eient reactions'
oi the less reacrive melal is the
limrting reagent' { A limiting reagent
thal the soiution of the sak be in large excess to
reacts compteteiy,
must
Fcr enthalpy oi solution experintents' the lvater teaving an excess of

ensure that all the solid

dissolves' .-,- -L- -.--e of the rperti
reaction
the other reagent.
t'"tuttui minutes before the start ^Fthe
r rneasuring
'f't "*p"'i"t
andforseveraln:;rulesaflterthereactionhasfinished.Themeasurementsare
theoredcal temperature
which is exuapolated to find the
useci to plol a graph,
rise. r t.-E*^-^ ^r,n il
r .oitinuutiv sririing the contents of the eripandta nitfOliiL;1'3
evaPoraron
cuP to prevent heat loss throush
; ;,;.;;; iie on trtt 'a

w'e i s h i n g t h e o'l
r
.onlining tht soludcn'
4 ;
Y, : 1' 91
This
.Tt:::[;: [',[:i:::;
gives an accurate va
il: ri
notwhollv accurate'
thedensiry of a soludon is l gcm-3
is
The assumption that
of the solution using a pipette
rather than a measuring "',illil: -d
r measuring tht uolrrn'"
be accurateiy determined'
qvlinder, so that the ;;;; lmoles) of
'otute.ttt'
' This is not necessary for enthalpy of soluiion determinations'

'the calculation is canied out in three stePs:

the reaction = m x c x AT
SteP 1: heat produced by
:t
' mass, m, is the mass of sotution in the cup' notthe mas of solirte
reacted'
'
I
@The that ofwater
is assumed to be the same as
The specific heat
"ttt't '"illot t''uut p'oduced isjoutes'
notki$outes' i
il
(4.18 J gr "g"1, ,otnt-unitiitt'e
l.r
ii
ii
skills t
324 tlnit3: Chemltiry.llborctoty
 *ilEffiRlr:F- . -ffi.

step 2: ainount of solute reacted = concentration (mol d,oj) x volume (dml

(For enthalpy of solution determinations,
amount of solute = mass/molar
mass.) ' .

" .; . ..

@The unit of volume measured by a pipette is cm3. This must be converted into dm3
.:J by dividing by 1000.
,i "-
jSeFj-r
t'.,, Ptoi'iua oitJrt
I step 3: *- -
rnoles of solute reacted
If there is a temperarure rise, A.FI is negati'e; if the remperature falrs, .\H is
rpositive.

lnstantaneous reactions
Neutralisation and precipitation reactions are insranranebus This ncionl.ygivesan
reactions. The
method used for following both types of reacdon is rhe same accurate vaLue for the
and is described on
page 90. amounts (moies) of
each reactant, but
Errors can be reduced by: also gires an accurate
rusing pipettes, rather rhan measuring cylinders, to
measure out the volumes vatue f*r the votume

'
of the rwo liquids. ( of the solutr'on.
r rnaking sure that one of the reactants is in excess. The value
of aH can then
be worked out using rhe amount in molcs of the
limiting reagent.
r for neutralisation reacrions onry, weighing the expanded polystyrene
cup
empty and after the reacrion. This is a more..accurate lvay
of obtai:ring the
mass o[solution than using a pipette and assuming that the sorution
ias a
densiryoflgcm-3.
! measuring the temperature of both liquids before mixing
and averaging the @ Ihereis no
' fwo values need to plot a
r stirring immediately on mixing the firuo solutions temperafure-time
r reading the maximum temperature reached graph because the
reaction is instant-
The calculation is carried out in three steps. aneous, so tfuere is
no time for heat to
Step 1: hear produced by rhe reaction m x c x LT
= be [ost.

@The mass, m, is the total mass of the fwo sotutions; notthe mass of solute
reacted. Ihe specific heat ofthe solution is assumed
to be the same as that of water
(4.1slg.t1-t;,sotheunitoftheheatproducedisjoutes,notkitojoul'es.,

step 2: amount of solute reacted = concentradon (mol

dm-3) xvolume (dm3)
...j..,. .

.@Ihesotuteusedintheca[culationmustbethatofthetimitingreagenL

Step 3: *- _ heat produced or Iost

, moh of solute reacted
t'
t, If there'is a tempe.rure n'se, aH is negative; if the te*perature
falrs, aH is
iI positive.
t,
I
I
Chapter I / : Labora to ry che mistry 325
;..
Titration techniques
Calculations bas€d on titrations will not be asked in Unit TesS 1 or 2. Questions
based on titrations may be asked in tbe Unit 3 test-
Tomake250 cm3ofa
Preparation of a standard solutlon sotr.rtion of co n centra-
In any tifation, the concentration of one of the solutions must be accurately tion0.1oo mol dm-3,
known, Ttre method for preparing 250 cm3 of such a solution - a standard I x 0.100 mol has to
solution as follows: be weighed out. This
- isthe is because 250cm3 is
r Calculate mass of solid needed to make a solution of the required ( a quarter of 1 dm3.
coneentration.
r Place a weighing bonle bn a top-pan balance. Press the tare button, so that the
scale reads zero.
r Add the solid to rhe weighing bottle until the required mass is reached.

remove the botrte from the pan and then add the
@n. Ustttayto do this is to
Jtia. cnedng ttre mass untit the correct amount has been added. This prevenb
errors caused by spitting sotid onto the pan ofthe batance'

: Tip the contents of the weighing bonle into a beaker. Wash any remaining solid
from the bottle into the beaker.
r Add about 50 on3 of distilled water to rhe beaker containing the solid. Using
a glass rod, stir until all the solid has dissotved. In order to dissolve the solid
completelS it may be necessary to hear the beaker.
I Pour the solution through a funnel into a standard 250 cm3 flask' Wash the
stirring rod and the beaker, making sure that all the washings go through the
funnel into the standard flask,

beaker, to measurethe volume of the

@You mustuse a standard flask, not a
sitution, The vclume of a sotution is not the same as the vollme of the solvent used to
make up the solution. Adding 250 cmr of water to the sotid r,*outd not produce
an -
accurate standard sotution.

I Add more distilled warer ro the solution until the bottom of the meniscus is

Ievel with the mark on the standard flask.

r Put the stopper in the flask and mix thoroughly by inverting and shaking @The same
method appties
several times.
using standard

Performing a titration flasksofother t

volumes, such as
The pieces of aPparatus required are: 100 cm3,500 cm3
l a burette and 1 dm3. Standard
r a pipette (usually 25.0 cm3) and a pipette filler flasks are accurate
r a conical flask to apProximatetY
.f 0.1 cm3-
The chemicals required are:
r a standard solution
r the solution of unknown concenEation
r a suitable indicaor
!: :

326 rJnir3:Ownistrylobantc{yskillsj - . .
it i
 :ii:rri..,.;: - : -.-

il,,i@Rrc twocommon acid-baseindicators are:

r' ' ' : l phenorphthatein, which is colourtess
auetir* .' ..
,
in acid sot,tion and purpte in
sotution
' -as the atkati is normalry added
to the acia,,r. lrip"irt iffi u," .
sotution furns to a permanent pate pink
cotour
r methyt orange, which is red in acid
sotutbn and yer.tow in" alkatine sor,tion
--'--:'- Jvse'v" -
the end point is when the indicato, go",
orr^gu'
The method for performing an accurare
titration is as foilows:
r Draw a small amount of one solution
into thi pipete using a pipette finer
rinse it with the solution. Discard the
and @ A pipette fi*er
rinsings.
.. r ii.
.u-sing a pipette fiiler, fiil the pipette ro rhut
the mark.
uottom of the meniscus in oa l';:#:J:ffi:t"
liquid up by mouth.

pltwar use a pipette to measure out the solution. Measuring

rytinders arb very
inacorate, whereas pipettes discharge the stated
volume to ari accuracy of+ 0.c6 cm!-

r Allow the pipette ro discharge into a washed

conical flask. when the pipene
has emptied, touch the surface of the liquid in the flask *irn ir,.,,p
pipene.
i,r,u
Q Never blcwthe
@ Ihe conicat ftask can be wet as this wi[[ noi atter the number
of moles of reaEent contents of a pipette
added from the pipette, but the ftask must into the conicai flasr
not contain any acid or atkati.

r Making sure that the tap is shut, rinse out

a buretre with a few crq3 of the other @Eurete: are
solution and discard the rinsings. catibrated in 0.1 cm;
r using a funnel, filr the burerte r. above the
zero mark and run iiquid out uniil divisions, buiyou
the meaiscus is on the scare. check rhat should estimate the
rhe burerte berorv rhe tapis filred with
liquid and that there are no air bubbles. vo[ume to the
Remove the funnel.
r Record the inirial vorume by rooking at where
the borrom of the meniscus is
nearest0.05 cm3.
on the bur.etre scale.
r Run the liquid slowry from the burerre
inro the conicar frask, conrinuaity
@Att readings and
the mean tiire must
mixing the solutions by swirring the liquid
in the flask. Add the liquid dropwise be recorded to 2
as the end point is niared and stop when
the indicator rnorr, ,ir. J'poin, decimalplaces or to
coiour. Read rhe burette to 0.05 cm3. +C.05cm3.
r Repeat the titration untir three concordant
tirres have been obrained. ( Concordant means
r lg-nore any non-concordant titres
and average the concordant varues, to give that the dffierence
between the highest
and the lowesttitre
Titration catculations is not more than
These are described in Chapter 10 0.2 cml.
on pages 20G11.

@ru1S, the equation for the reaction is normally given in the question.
Lookatit
..
retulty to fi nd the mote ratio of
the tr,rc rei cta-#]ri in. ;; ;;; ;;;:,
you must write it before starting
the catculation "r.,,.",
Rememhrthatthecalculationiscarriedoutinthreesteps.

step l:.calculate the nurnber of moles

in the standard solution used iu the
titration.

Chapter I 7: Laborotory chzainty 327

I
t' ' -
l:
,g
.,. @Ooittrgetto corrcrttrerotume(pipetteor burette) fron tm'b dd'
.-...: .. , vokmeinco3 ' '. ::' l':'.::

Step2:usethestoichiometryoftheeguationtocalcrrlatethenunberofrioles
(amount) in the o*rer solution used in the titration'

.@tf th. mole ratio is 1;1, makesuredratyou state thattie.nu$lof

rUsln tln '
numberof mottsin thefirst soluiion.Ifthe ntiois not
rE*A *Ution equals dre
tl, make sure that the ntio is the right way up in the conversion:
numberofmotes ofA in equation
motesofA=motesofBxffi

step 3: calculate the concentration of the second solution'

@ilake thatyou giveyouransvrertothe correct number of significantfigura'

sure
tiln aoubt srve it to 3 s.f.

Worked exomPle
was weighed out'
A sample of Z.OSg of pure sodiumcarbonate, Na2CO3'
cm3 in a standard flask. some of
dissohred in water and made up to 250
this solution was placed in a burette and used to ritrate 25'0 urf portions
are shown in the
of h solution of hydrochloric acid. The titres obtained
table.

The equation for the reaction is:

ZHCI + Na2C03 -+ 2NaCt + H20 + C02

Expcriot€nt Tiht/cml
7 ?2.35
- 2 . 22-10
3 27.85

4 ??.50

a Calculate the concentrarion ofthe sodium carboDate solution'

b Calculate the mean titre.
c Calculate the amount (in moles) of sodium carbonate solution in
the

mean titre.
d Calculate rhe amount (in moles) ofhydrochloric acid that reacted'
€ Calculate tle concentrarion ofthe hydrochloric acid solution'
Ans*er
,- rofrt *rtt of sodium carbonate= (2 x 23.0) + 12'0 + (3 x 16'0) = 106'99mo[-l

= 0.0?50 mot
amount of sodium carbonate =
#H* = ,;ffit,
mot 0'0250 lot - = 0.100 mol dm-3
concentration = votume- -
(zso/rooo; Um'

38 ltntt 3:Oreirbtty l&Qtory s*i(t, -

 mean titre = =22-4? cmj
c amount of sodium carbonate 1 coricentrat'on x votume
dml
amount= 0.100 mol dm-3 *2?'4? = 0.00224 moL
looo
ratio HCt:NaeC0, = 2:1
amount of HCI =2- x0.A0?2a mo[ = 0.0(X48 mol
1

concentration ofhydrochtoric acid =

mol ( uot tt"trltvotumes
ffi were converted from

- - o'oo448mol - =0.179 mol drn-] cmi to dml by

dividing by 1000.
(ri.o/rooo am3)

Evaluation of error
There is always a built-in error when using apparatus such as balances,
thermometers, burettes and pipettes.

The pipette may be stamped with the volume 25.0 cm3, or the balance rnay
read 1.23g, but these quantities ar-e aU subject to some error. For example- the
manufacturer of a balance may state that the mass of an object is accurate to
t 0.01 g. Therefore,'a reading of i.23 g may mean a mass anywhere berween
1.22 and 1.24 g.

If a container is neighed empry and then reweighed containing some solid, each
weighing would be subject to a possible eror of t 0.01 g and so the mass of the
solid could have an error of t 0.02 g.

Worked example I
An empty crucible was weighed, using a balance with a possible error of
1 0.019. It was reweighed containing some solid metal carbonate, MCO3,
and was then heateij te ccnstant weight. On hearing the metal carbonate
decomposes according to the equatidn:
MC03 -+ M0 + C02

The readings were as follows:

r Mass of empry crucible = 14.23 g
r Mass of cmcible + carbonate = 16.46 g
r Mass of crucible + contents after heating to constanr weiglrt = 15.61 g
a Calculate the mass of carbon dioxide given off
b Hence, calculate the amount in moles of carbon dioxide pro.luced.
C Calculate the of metal carbonate taketr.
mass
d Using your answers to b and q calculate the molar mass of the metal
carbonate and hence the molar mass of the metal, M.

Ch opt e r I 7 : La b t ratory ctranistry

,7

.. .- . .' :

e Assuming all dre measrremens of mass ha( an uncertainty 9f tO.01 g,

-eAorl.ru th" uncertainty in the value qfth€'molar maS of M; : ' :
Ans*er
a mass bf carhn dioxide = 16.46 - 15.61 = 0.85 g

h rgL- 9 0'tu '=

4neun1=-- =
molar mass 44.0 g mor'
, 0.0193 mol

c masi of l,lC0r= 16.46-74.?3=2.23 g

d amount (moles) of 14C03 = amount (motes) of t0, = 0'0193 mol

mass 2-23 q
s mo[-t
molar mass of l,lCO, =
;#k =
;ffi;='116
motarmassof H=116-[12.0+(3x 16.0]]=56.0 g mol 1
e mass of C0, = 0.85 t 0.02 g
The amount (motes) of C02 lies between 0'83/44.0 = 0.0189 mol and
9.57144.0 = 0.0198 mol.
Since the ratio of l.lC03 to C0, is t:t. the amount (motes) of MC03 also lies
between 0.0189 and 0.0198 mot.
mass of l.lC0r= 2.23 t 0.02 g

=11e s mo[-r
maximummolarmassof MC03=
#ffi#*=#*
Therefore,
1
maximum molar mass of M = 119 - 60.0 = 59 g mof
smallest mas 2.21 @The etement' M'
. minimum molar of Mt0: = = = 112 g mo[-1 be(r, Mn" Fe'
coutd
mass
;*;;ttt 0J198
Therefore. :"ril,T.ttlil',
minimum molar mass of= 112 - 60.0 = 52 g
M mot-1 the range 52 to
Theuncertaintyofthemotarmassof Misthatitisbetween52and5g g mot-l' 59gmot-r.

Worked example2
A thermometer is labeiled as having an accuracy of + 0,2'C.
In an enthalpy of neutralisation reaction, the ternperarure before the
reaction was 124"C and after the reaction was 24.5'C. The mass of liquid
userl was 100 g. The specific heat capacity of the liquid is 4.18 J 8-1 "C-1.
Calculate the percentage enor caused by the thermometer and hence the
error in dre evaluationofthe heat produced

Answer
temperatureriss=(24.5 -17.4)L0.4=7.11 0.41 ' ,,

-
1!
percenta ge error caused by the therm om eter = t0.4 x = ts.A3%
7.7
eC-1
heat produced = 1fi) g x 4.18 J 9-1 x 7.1T = 2968 J
error in vatue of heat produced = +5,67'/o of 2968 J = 167 J t