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p (~N\Q'OJ A~Cl_~ C\A~

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sheIN. .

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, Thermochemistry

.: i: '~: .~.~'~' .::f _) '.: ,1 , r . ->. ," :. : .. " :

Therrnochemi:;;,try is concerned with en t ha Lpy. (heat) changes that- take

-,;.i. ' :."_ '''':. J.. ~.: " ."..: .";_ ~ : :,". . '. . _. - - . . . .

'place 4uring chemical'~eaction~;~Nearly every;che~~cal'reactionis

~ _- -'~. ;'~"", '" ·'.;:t : -'-:.', ; =>: < " 1 : :.: .;' - _. " ..' • -., • _ ' - -', • -, :;. _ • ".

accoJJlI?~p1.ied by the abso'rption' o r-v evo Lu tio.n<;:>f', hea t •. R~aotions' taking'

in he~~ as~ i;h~'y"proceed arecal,j/edENDOTI-::ERr'~IC .r-e act.Lon s /"thos~;' giv:ing

. - . . ~. . _ -.l.' :.: ", . . " .., _.. . __ " ..

out heat as they proce'eda!'e' c a Ld e d 'EXOTHEI,UJ1IC reactions.

:B~fo.re we, proceed any further we shall look at the q u e st Lo n "t-ilia t

is 'the' dr~vin~' :rorc~o:r a 6h~t .. ticaa.. r~action~tf-A sPoNTAimoD8 ii.E~CTION may be~~garded' ~'s"oh:e.':·whi<i:~hhas·,the'p;tenii.al,' to p,ro.~eed ,wi t~out . the' assistanc~:~f';~n ·~jc'ternal.-agenCYtSpontane(jus· mu s t ~ot 'be confused W'1 th . instantaneous.An instantaneous reaction is one wh i c h happens "in an

- ..... ' ,.\~ ..

1

instaIit'" or ve':Jyqu{Ck1:Y~\4he'reas'a,sp6ntaneous reaction can happen' quic~~y or"slo~lY •. Thl1~' i tis po s s Lb Le .f'o r- a reaction to ,be ; spontaneous andy~t p r o c.e ed at such a slow rate 'as to appear' to be almost XlOBex;i,.~ten{,;'eg.the iarrtiliar'c;6~bination of hydrogen' and oxyge~. On the addition of-finely diV-ided platinum' the cOrhbination beco~es" explosiv~

:::?w~d~!1t::~~::::~;s~~~nttli"t ·the reaction remains spontaneous·with

lp. our search :for an answer to the questi~n "1Jh:at is ,the driving

;'.':~-. :~-r~:<·]!f;.:·:·:··.:- .. ' :, .... ,. . .

forced£' a chemical:re'act'ion"l'" we

may

begin vii th theexaminatiort'of the

factors' d~t~rn;'iriirig" the direction of spontaneous change .. It' is' the direction of spontaneity which is one of the most important features of a chemical reaction. Consi~er the following simple examples of familiar s po n t arre osa s: p.r,~;ce-s,sesand attempt to find out where the r'eason for

itse ir '~po~t,qn~ J,. ty: ~ 1 i e s •

• • ~ -. '" : • ~. • '" : • : f

:: >n:l:t€r poured o u t, of a glass at the top of' a hill f'Lows downwe.r-d s s.

This process begins as· S0021 as the wa t e r- is poured out of the glass and doesn't require any further external assistance, thus conforming to the definition :ff sPdntaneity.suggested above.

NB~~ The rate at which water flows is determined only by the angle of the slope anditdoe'~riLt affect the spontaneous nature of the

. ;~,

process, for water will always flow .do~n~a~ds no matter how steep

. '.' .. '~ . ..;. ~~",' .'- '?~~~~-~1' ~ '-~ .: .~.:~.. :

the ~lope ..

a sto!1e,willfall

, •...

a s~~et~h~d piece of-ela&t~c will ~6ntract

, . i'. when<releaseq..

All tii.esetnay be des'c~ibedas spon't'~nyo\ls, p~o~ess~s ~ fo~ they occur of their own accord 'ire erie di:t>·e'ction.ori.l'y~

-''''<:~:'AithoU:gh thesi?styonta:neou,~p:r9cess~s)nentio:ned never reverse them-

..' , !' ' ,

s el ves,th~iy 'cari bereversadby, app~yipg i~n ~~t~rnai a.geri c y,

:' .- ·· .. n~ ~ ". . .

A spon,t'aneous' pro'ce'ssi's'bfi,ts«:l;f,' ;~~r~:r,eye~s,ible, ,~ridcan be reversed:

only wh en work is d~ne .2!l the s y s t.em -.

Looking closely at each of these processes we can see that a common

2

taneous

po t eri t.La L energy_ in the direction of spon-

0 __ .,_ ......

change .. This energ"y:',mayb~ lost, r'pom ~tp~,~system.k.ndut::i.lfz.ed to

in

feature is a net decrease

of' s o.m e kinq .,,(ap ·:elas'ti.c ba~qmay, be used t~drive' ;an ae;~~iane, a \'Jatchkprirl~- ~:~~~ye,.s:, tht;l, hands~bf a wat.ch),' or;t may be convert;cd into ano'the:r" fO~:~~_'~'~~~~'~y :, (K:ln~ti-60-~,~ergy 'in' the' cas§> of the water and the

faLLi1'ig_stone) •. __ .,.," ' .-_, : ,'t', ',:" '

'As the'~esult o.:(tl~eabove;.:.''''B--.may 'now.perhapS suggest that a chemical

14 '.'" • • '. • • • • • ~. .'. r ;.;' " .' :.

reaction 1vill be spontaneous in' a given direc t Lon oy;;cause 'in.p:~ssing

from reac'i~~is to p~o-d~cf~-:_a:',:-d~t~~ase~~':in '~otel~tial' 'energY-.'has·taken·

; "

"J'_ '''-:'. • .,~"'<o.J" . • •.• _

]~ow.' if there- i's' a decrease' in. p~tential.;~~er;;;· 'in~ p~s'S.ing from reac-

tants to~~oducts9

',:,- .: ..

then thi.s'€l'l:ergymust be lost from the' system in.

some waY9presumably ~s.heat.T6wardsthe

end of

'<"rv

the nin~teenth ce~iury.

,~- .,. .

i: '

Thomsen and BertJ:?,elot sugge~tedthat the, : change in. energy as measured

by the l-i~a t' e vo L ve~ in a chemical react,ion,vas _ the dri Vil~g' f'o r c'e behind the reaction. To support. this they we r e . able to .ci t;e many r-ea c t f on s in

which heat is evolve~ in passing from reactants td productE~

SucrCreac-

tions areex6ihermic reactions~~

The decrease in ~I.le.rgy :~n passing from _ reactant.s to p r-o du o t s 'may be

illus tra ted for _ any ex?tl'1'ec:'mic -r-e a c tion as,

t' '

~p. . e n e.r-gy d~~~g.ram 'as" b eLo w ~

To tal energy _ Er '-, of r-e a.ct.arits

."' ..

----------

/Ep - Er.=6H n'i'tenergy ev0l;-ved as ,heat in the reaetion •

. '

Total- energy of pro9,ucts

Ep

Re ac t anc s

Products?

Re a.c tionC,,"'ordiria te

the ~ota.1. energy change-for the reaction. It can be- seen that ~he

valu~ of~H depends only ~n the val~es biEp an~Er. It·is independent of 2:::1y intermediate stages,,-Thus-the proposit:ioii that ,the driving force b e h i.nd a c h ern Lc a L reaction is th~ decrease in ~nergy in 'passingfrom-

, . '

reac.tants to products s e em s- reasonable on the -ev Ld en.c.e presented so far.

. ;" .' ,-, .

. '

But meny. spontaneous cb.em i.c a.L changes are accQmpanied by an absorption

of ::-leat Le , there is an iE.2rease in the total energy of·thesyst-em in

--

passing from reactants to p'r-o du c t s , Such reactions are endot~errrlic 9 as

represented by the fo~lowi~g diagram.

1.5'"

--

;~:~~!n~t Er I

- • .' _, • I

,,--;

'I'o t'a L energy 0 products

....... ---~-- -

'. -:~

'net energy absorbed, as heat -: 'froin the surroundings by the reaction~'

_Ep

Er =/\ H.

" -:'_

Total

. i '; .: -

.; ~'. .

"; ..

Re a c t arst.s "

"Broducts

-:-' -- •..•• "~"--""';"'>-' •

It thus ~ 9comes ,,>bvious tr-,a t although the, decrease .d n 'energyrr:ay be

React~on Co-ordinate

a contributory fac}o!~o t:'l~ ,ci1:~v,ing; force behind the r-e a c t.i o n it is

not asuff'ic~elnt on e f'o r+a Ll, ca.s e s, , pa r-t.LduI a r-Ly endothe'rmi"c ,1 ';2 ... ;t.ioris~'

'J~"'mu'Elt' no VI, look, at moro spontane-ous. reactions" or. pz-o ce sse s, p e r-h a p's of' ~'dif~'8r~~t';~~ind~ to,cii:~'cover wha t 'ot1J.er f'actors1,may ,be, invo'lv:ed~

" .~. -"':~ '. " _. . - " '. . . ."_ .

0i~6e ~y,jo·2::;.ave alrea(:fY,€}tEj,blis1;led the energy f a c to r- insp'orI'tan\~;bu'S

reac~,ibhs:?'::It ;';~ c'~~~~~i~n;'-t,~ lo~'k at systems wh e r e .. the,rei~: 'little or

: ',:) ': .. I: "':~ "::; '-'j: :_- - .:,- :. . .. ', .~ .. -:. . _," '.. ..

no change in total energy Juring , the reaction.

~, :: .... ':, ::- .. . .'.~. '~-._ ;) '. _; ,'~. : -: t:' ~.~~ .~ .. -; :.' . .' ':f: <.':: ~ .,

A 'Eiy-§t-em 'in 'ltlhich the f »t.a L 'en'ergy: rem~ins c orfst an t is lcn ocm as:.an~;

isolated s y s tern, COyt-s"iqE?F ,'~wq",gase:Sr$el:)'ar'a t e d by-a par;t'i~,tio;n i~n, a];'aggeci '

,r,~·:·::·~I~' .. rr: •... :~."::;~l·_r._~ .. ::}:(_j ..... ,> • •... . '. •...• ..'

cori't ai n er' wh i c'h 'is· cLoeed, ie-.no change. in .. t:ota:l. '.e~"l,ergy-of the,.:-sy.~stern~'

,~ •. ; .j. • .,',.:.:.::_:,::',:",'",~_';"~: -·~ •• t.

,~. ,.:.: :~,_1:~:::'::'::;'-:_:"':., _.--,.: -. ---

..... ' ~~- .

. ·-~t:r:·:·: .... '-:": .. - ·r.· -:"_. f··-:;.:·_'_;"_···"" ._."._,-

" r' ... ._-...... '~ .. ~","." .......

•. -. •••• J

; .', t ~

<'/'

The t,·;o g2~S e S,' ii a It and" lIb It

. ~. .::., : .. ~~ _} ',.: ..

partit~oQ ~iffusion of the

:tart 'as in A above. Upon rem6~:al' of' the'

t~o ~ases06curs and ~~' ~ri~ ~p!with the'~~t~

uation as

in B. Th.e' ch arig-e i.s apon t an ecui s .e.s ,:tt begins "as soon ''as' t he

partitio:::l

,- ,

is removed9and ,.t:ipi;rr.~vers-,;ible~ Thesystei11:{s:'becom±n'g

more m'ixed-·lxP.

~ ~. .-

': .. '

i:Je may rrow formula te 2.n,~ther pz-o po-srit d o n '-concerni.,p:g ,the~n'atur~t:'i)f .. -. :-,

, .

spontaneous p r-o c e a s e s , The::' e i sa, t ~~ctenp,y" f'o r,'" the.? Y.? ,t-B__iil:' td~ .. h.ecome' 'ruor,e _.

:j s,:~:e:;: :e:~rX ;~::y a d::::::~:;e;;~::'l:::~~:~~:~!=:!~i~:::;/~~:t~

s y st ern ~as .10\'". el-lt~C>1?y,~,Jt;~:u:r:e.,S~YSf0:3cJin~l; s~bs,tanc,e a t'.absolute .z e r o : r.'. of t~~.up~ra t~~~~"'has . ~ero '~~~rop;y •. Eoni a Spol';.t:aneousth,atlge">:i.n'''i2n.r:tsolated

sy~t~m there must '~e:~n i.I1:-ir~a(3iei.,~;;eIftr.()~y. ·1.'be tin:inre'Ts'e 'cl§:ybe 'COl~sidered as an isolated sys':em of constant energy. It follows9therefore9

~6

--

4

that for all changes in the universe taken as a_whole there must be a net increase in entropy, althougt in different parts of the u~iverse there way be'changes' taki.nG place wh;f!ch involve either an increase or a decreas e in entropy, or rio 'ch:?'Ilge ~~ .. Thu!s 9 .•. a L though the energy of the uni v o r s e is 'constant 9 the on t r-o py unu s t continually be increasing.

The directi.on of e pori t e n e o u s change ~s governed by these two factors ~ .

1) change in- enthalpy (to~al ene~gy)

2) change in entropy(discird~r)~'

A new function 6. G (change in FREE EHERGY);i"sde,fined, this n e w function incorporating both the enthp.lpy and entrop.y'changes.

r

1::, H 'i'L:1s I

---'---~---'

T is the. absol:ute. t5'uperature.

The product T uS .( also an energy term) ll1easures tne"t-li'ange in energy wh.i.e h takes place. as a r-e s u L t of the 'rearrangement of' the: cort~ti tru en t;' atoms e . rb.i·s.lIinterna~11 c h arrg e in energy is' a Lwa'ys contained within the, system,andls therefore DeJer ava~lable t~ido ~cirk ouiside it.~G is therefore. the, d.i.f f e r-e nc e b~t'\V'een' th~ total energy change and the

'".,. ."

l!Iunavailable" . ener.gy c harig c and is thus a measure of the energy which

~. available to do work outside .the system,ie.

a measure of·the free

ener~.

-"Je. are now in a posi tio;J.to suggest an answer to the original question tlvJhp,t is the driving force of a chemical r-e a c t Lori v "

Thedri ving force fora,spon taneous c:hemic~_l ·reactiQu.._i's the GeGPGase i.n, free e~rgy which ta·_:es place during the req,cti,on.

~tan~ard Ehthal~y~(Eea~) Changes

There is DO real merningto the value of a heat change unless the exact. conditions und~r whiCh mea~uremenis took place ar~ cl~arly stated. It

;

is important to, state- phys~cal conditions of reactants- and products.To compare heat changes of' different reactions, or to make use of heat c harig e s In thermochemical calcuLitions 9 it is convenient to quote the

. . 0

magnitude of the heat ch arire at a chosen temperature, usually 25 C.

vlhen heat c uarig e s are m e a s u r e d at 2'50 C 9 the h e a t change is' said to be a Standard, h~at change. uE'uallyd'enoted by D. H()-.

Some SpeGial Enthc:-.'-py (E~at) Changes J),Stan,9..ard Enthalpy of' REaction

"Th Ls may be defined as the' e~thalpy change wh i.ch 'takes place ~t 250 C when the. reactants and pro::iucts are 'in the' mo Le propo~tiohs as indicated by th'e e q u a t Lo n. for the re:lction~(If'gciEies'a~e'irivo'lv'~d in the reaction, it is usual to stipulate i-"at the~e '~h6~ld:;beat one at~dspherepressure~.

- 2) Standard Enthalj:rY~ ofF6-~rriation

This may be::-d-e.i':ined as'cheenthalpychange_: l.;l-~n on e mole of.:'che compound is formed from its elements in the standard states. tItls convention to' take the a ct i __ laThea::tcont'e'ilt of all e Lemer. t s in their standard states as zero).

3) Standard ~ntha.lpy-of CO:l~b--us tion.

This may be d e f Ln e d as'~he enthalpy change wh e n one mole of a substance is.completely "'buFn-e&·-i-n-;,-Oxygen under standard conditions ~

4) Standard-EnthalpY o:fNe:,-t~alizat,idn'

This [.''lay'be d e f'd ne d v-as -o-he--enthalpy change (heat evolved) v/hen that

aDount of acid or alkali needed to form one mole of water is

neutralized,

,',

under standardc~~dit{ons: ,

5) Standard _.:Gnthalpy 0:t00~,ution

This ma y be' defined as -'~he enthalpy change wh i c h takes place when

one mole of the substance ~s completely dissolved in a large enough

v o Lum e of wa i.o r- so that no' r'l.J,rthe,r .e,n~~~1:py cu_ange._.takes,-place 9 Ender standard c o n d i, ti i o n a , L'he so Lu t i o n is now said to be at inf'ini te dilution.

.He s s t s La.w. Q._fGons,tan,tRe .. ~"t Summation

If a systemk isconver-'~ed into a system B, the enthalpy (heat) change

i. independent of the meth0d of passing from A to ~.

ego From ammonia gas, and hvd r-o g e n chloride gas He can mak o a s oLu t i.o n

of ammonium chloride in t,1:-/) ways.

1) React the gases and dis~olve the resulting ammonium ctl~ride in water.

2) First dissolve each gas in wa t e r- 9 and mix the two s o Lu t i.o n.s ... From He s s ' s law the e n t h a Lrry change is -(;r"e same in bo t h cases.

1 )

NH3 (g) + . aCl{g) NHL,CI ( 5) -'.- a.q ,

.~H4Cl{S)

N,HL' CII ) ---------------- b k.J

;. \aq. '

H

------------------ a kS -,

Total enthalpy change = (a+c) kJ

2)

>

M-I-f3 (aq.) ------------------ x l~J y- kJ

Nh3(g) + aq. HCl( , -'.- aq. g,

NH ( ) -'.- HCl( )

3\aq. aq.

scr. ) ------------------

\aq.

--~ NH4CI ( ) ---------------

,/ a q ,

z kJ

Then by Hess's lawg-

=

(x+y+z) kJ.

The I'orn-}:a-ucr Cycle

This is a wa y of expressing tt"e first

6

- ".- .• <..._;:.. _'

.. -- ..... - ...

law ;o:f-the~i~lOdYh~I:l~.ps~. wh i c h

e t a t e s e c- The -total amo un t of ene~gy in an isolateq. system remains c o nst an t. •

Probably the best way of 3tudying the Eorn-I~ber Cycle is to have ~

look at a question involv~ng it.

~ .. _ -: , .... {.

Q) Calculate a v a Lu e fb'r -;:;1-:8' la}<,ticeenergy> o'f,"";p6'e-a:'Ss±lim~:chlQxid,e

'!. ...

u.s Lng+a ·.sui-t~ai)ie therEwchemic-_al cycle -<;ansi.ti-~e folloVlillg data~-·'''·

:-,-" . . . . .

~ ..

enthalpy chal-:.g8 of atoE1iz~tion' of'p6t;Y:U3'siuE1- .... - ... ..:. __ -_-;- _

• '. '.1 '.

, "'1 .: +90 kJ 'mol- .:

first Lo n i.z a tt o n energy of potassium

~----~-~---~~----

J. - 8 'T 1-1..

:!:+~; I. Kv .. mo ~ '.

.. -1

,=+121 k J Dol

e nt h aLpy c~'Carig8 of a t orri.z: ~ tion (per rn6i 6f'~hlo~in~:ato~s)

., . ~-.:.-~- ~

of

chlorine

electron a~~inity of. chlo~ine =-J64kJ moi-1

;ie. er.;,thali_J'y c h ari g e for t~,~ 'reaction'~_;' CIt" \+ e- Cl-(g)

. . ,\g /

enthalpycl':ange off'on::at~.on of' potas'siurt:':"ch±ori'de

, .

..- ·-1 ---- = -436kJ mol

....

..... 121

II" ,I

kJ; ,,'1_ a,tomiz,:tL'n ; , . .c h Lo rvi n o

, i

-,' I

of

36L~ kJ

: ! s :~.

1:":'

~lec~ron_affirtity of' chlorine

s,

+ ~

h(' ),,: + ,z-,Cl rI ( )

g . '/<\.,::;,\g .

(

I

,+ Lq8kJl :first Lo ni z a t.Lo n energy:_

I . 0 f' 'l~otas' i urn

't r .~ .l('~ ,

f': ( g ) 2 v i~- 2 ( g )

l" ."

I

+ 90 kJ ihBat of a omization

1'. O£'pQt__qE; . ~UJTI

,j.

....

-',

kJ

. - ... - .. -.~.-

'La t t.Lc e' energy

, of'

1 . . ......

x. ) + 2C12.(g) '\s

potassium chloiide

Initial State

enthalpy change of f'orcation -Cil"""po·t 2. ~. s i urs: . .ch.L o,"-~ ide

I~c)_{s) I

____ _J

.....

... -. _-._ -', ._._

Applying Eess's law,

'(90' +1£--8- + +2+-:-6H

~. L

=: (-Li'36--':_'''9CY-_;'' ';'1"8--"""+21- + 36.4 ) kJ mol-1 -1

= -701 kJ mol

364 ) kJ

1

Dissolution of an Ionic Compound

This can be represented as belowg-

/\ !1solution

D Hsolution

=

+

o

Thus an ionic c o mp o u.rrd "Hill dissolve if the hydration eEergy is

grea ter than tl"-e La tt Lc e 2i'lergy.

1

Factors Affect:7g a Chemi~al Reaction Such factors a~e~~

h~s Pg.. 349 Chap. 15

(a) h e a t f t.emp e r-a t u r-e ] C) light (d) concentrat~~n ; (e) c .talysts

(c) physical state (f) pressure.

This a f f e c t e '.:loth the v . Lo c L ty of a c h erc i.c a L reaction and the final position of equilibrium. ~or a lOoC rise in temperature the rate of a chemical reaction is abou~ doubled because there are far more molecules

possessing act~vation enc'gy----haxwell distribution curve.

2:ffect on _the "posi tion o:f Equilibrium

?efore we can consider t~ s we need to be familiar with reversible

(or bala~ced) ~eactions.

Reversible Rea,tions

Conside:c t h. reversibl-, reaction for the lIaber process for the

manufacture of' ammonia.

Ii r- / \ -}- 3H2 (9:) '-.. .___:

"qg) :s

; I~ II

=

_1

-92 kJ mol '

A r-e v e r-a Lb Le, reaction ~ s one whe r-e the products of the reaction? (aEL'TIOnla III th~ above c a s -. ] , onc e formed, react or break down again to give t~e re~~tants,(nijrogen and hydrogen in the above case).

In a reversibl~ reaction, the forward reaction,

in the above case,

and the backward reac:ion,

2HE3(g) -~ N2(g) treated se~:'arate..lyo

-}-

in the above case, can be

The gres.terche concen ;ration of reacting substances,the more

collisions per second, the more fruitful collisions per second, and

the faster the reaction.

If we start 0ith nitro en and hydrogen molecules in cur reaction

vessel ,the 8p6~d of t~e f 'rvard reaction uill be high to begin with

and gradua~ly f~ll off. ~~e speed of the backward reaction to begin w i, th ~'Jill De z@."t'o ,and ,zr2 '~ually increase as o:~ore and more ar,:'E:onia is

formed. If the ~'orvlard re '.ction starts off' q u Lck Ly and SlOHS d o wn , and

the bacl:''_''Et::.~j_ r@..3.ction s t.a -t s off at zero spe ed and quickens up 9 a

point i.s rC3.ci'@.d wh eri the f'o r-wa r d and b a cl-.wa r-d reactions are going at

the same speed- At t~is ~ int the ammonia is being produced as quickly

as it br-e ak s d(\.own. He rro w Lave 2. state of DYl:JJ,.lJiIC

EQUILI:S~_IUI"1 and the

compositio~ of ~he mixtur (ternperatu~e c04otant).

This c h+.Ln of events l." to the arrival of a state of dynamic equil-

from this point o nwa r-d s 14il1 re;'aain constant

111 I ' ~"'2' ~ i \Si

... .)'~ ."

2Nlf] Cg) . + Heat

r------...,

.. -
20 N2 aS5une another 17 N'
2
J N mo.Le cule s ; ..
60 H2 2 51 .{
-- have reacted ~ ~-2 ,
20 Eli 26 hTH]
-" ] a s au.ae 10 ;N2 mo 1 ec u Le shave

" ' .. _. re act e d -,--/--;,!

o Ell':) _}

time c d~'yo time =···10 day::::; time 20' d2.:ts ... ~ ..
.- =
~ :::: 20 RF =:: 14 RF = 1 1
.r'F
R~ :::: 0 R'Q = 7 RE = 1 1
.b !..J Thu's'; a f t e ;' 2G days for 0 v.:t' reaction a.b o v e , -d'yrramd.c eql..dlibriumhas

2

, .

K (temperatur~constant)

K is known as t~"e EQUILIBRIDr11 CONSTA:tTT

T~'ler l brackets above "can "conc-entration". __ l

'I'hel~e

is

r ,.'

P:f'i(\Clple called Le Cha teli er 1 s Principle,'

vlhj_c~ ::-,ela-:~G:-j ~.J a rever['\.:::>le reaction once eq u i.Ld b r-Lum has been react-_ed,l--e. C'V\o..telier' s fn.nciple e t.a t e ss c-

Af.~$:pm~ihing is done to. a reversible reactior190nce equilibEi:££l._~pa~j')e<?}.!-_Teached9 ttxQ". composition of the m:txtur~ w'ill alter to

Th-<..lS app~LTLn5 th;_s :Jrinc\:ple to tD.e Haber synthesis 2.00ve 9 'He have g-

I:f the:>30perature is iricreased9

the comp6sit~o~ of the mizture will.alter to reduce the teuperature in a c c o r-d an c 8 -;ji th Le Ch~telier' s Pr-ri n c i.p Le 9

t~js can be achieved by temoving the heat9

t h.i e is a c h.i ox .. -ecl by: ,8orc ammonia b r-e ak i.n g d o wn into n L t r-o g eri and h yd.r-o g er,,

In near~y all balance~ reactiops9 the equilibrium BOint varies with t emp e r-a tU::'~8 according to t"."" Cha t.elier' s P:I;?inciple.

The exula~ation of th~ effects of a change in teDperature on the

",

po-sition . o:fec:u~libriufd·o.~~n lies in the change in the number of'

mo Le c u Le s possessing activation energy. In a reversible or balanced

reaction there ~~e differ&nt activation energies for the forward and b a c kwa r d rQ.D_c-Cions.

32.

--

Raising the temperature increases the number of molecules possessing

these activation energies~ but the number is not increased;-in the
same proportion in both cases. The larger the activation energ~! the
.'
larger the relative increase in the number of molecules having t h e activation energy.

R ..

F

", ,

2HI

; 6,. TI =

-11 .;3kJ 'mol -1

ego

+

'R B

A rise 'in temperature increase~ RF and.RB but increases~B more than RF• Thus" thehi'ghe:r the "temperature th~ smaller the ·ra of HI molecules in themiiture~

The 1£ of HI molecules in the equilibr~um mixture is 79% at 40006 and 76'f~ 'at'5000C~'" ... _._ ..

The f r-ac ti.o n o.f. .. the .to.tal number of mo Le c u Le s having an energy at least equal to the activation energY9 E9 at kel~in temperature T~is given bye-E/RT9 wh e r-e e is the base of natural Lo g s v v Rvds t.h e+ mo-La r-

.. . . 1 1 . - .... - -" - . . _._ ......

gas const'ant ·(8.3 Jmol- K- ).The·above expression is called th~:'

.. " '.

Bol tzm'ann factor. The activation energy for .thecombina tion~ of Iryd r-o g e n. and iodine at 4000ci~ 174'kJ mol-1 and so the fraction bf m~lec~le~' with this energy isg-

2.72-174000/8.3 x 673

=

.r ~ ,

The activation energy f'o r- the" d Ls s o c La t-d-o nve-f HI is 185 kJmol--1•

The .t.a b Le b e Lo w Sh01;/S' values of the D6l tzmann f'a c to r- for the two values

of the activation enB~gy ~t 4boOc and 5000C~ ..

/ -1

E kJ mol

174

' .. -.. .." _ :"'4troO C·

''':'14 3 x 10

5000C.. . 170 x 10-14

185

,"

.. .. '-.;1 .5

300 x.l 0

.' .x . .... ~ -- - ._ . __ ".' .....

Thus the. larger the acti. .. va tion . energy the larger the relcHi ve incre~se w'i th rise of temperature in the number of molecules possessing this

energy.

(b) Light

All radiations from X-rays .to Ln fr-a.r-e d can exert a chemical effect.

Photography, wh.i c h is based on this f a c tr, :-:l]:tkes use of the susceptibility of' silver halides to the action of these waves.:Some reactions are accelerat~d by.ligbt9 eg e , the decomposition of H2029 the combina tron. of H2 and C12; the, substi tution of: hydrogen by chlorine in CR4·•

Consider c h Lo r-Ln e (or bromine) combining 'IIi t hvh yd r-o g e n , The reaction is different to·.that,between hydr~g~n and iodine. Th~'rate of the reaction between chlorin~ and hydrogen is not directly proportional to the concentratinns of hydrogen and chlorine, but depends

4

on the intensity of light. Nernst in 1916 put forward his theory of a

chain ~eaction. He put forward the theory that the ~bs6rption of ~ suitable quantum of light E?_ne:r:gy b r-e a k s the bond b e't we e n ~he two:at.oms

'. . . .

in the ~hlcirine molecule, producingfr~~~adical~ (chloririe at6ms)~ __ ~_

. :.

C1--'C1' +

. ~ ..

h v ---------? 2C 1. •

h,is Ple.nck's·constanty andy.i;}3 .. _~J:l.~:f£equency of the rad~?otion>~The freeCl.al.,:,e_ve~y·:'r·eacti~-~. and react as g':_'

.. . ';_. ~' .. : - . -~---. . . ' :_! . _ .. '

_____ .... . "

__ .: tel. ;0:+ :R~:~:' -) HCl +

+

C12_ '.-. --'/-?'. JIel

----------~~-----------~(21

.,"

-_.----:...-.:...---:;,....-.-------..;--~( 3)

Steps (2) and (3) are repeated over again, so t~at the absorption of a single C11...~'antum of light energy may result in the combination of

: .

many tho~~ands, of H2and C1.2 molecules. The se'qu eric e is eventually stopped who n t wo free' r-ad Lc a Ls form a s t a.b Le molecule s

ego

-+

Evidence for the Above

Uhen chlorine gas is exposed to ul 't r-a vd.o Le t light,' theE/as. sho1.ITS the absorption spectrum of a tordc c h Lo r Ln e , Alsoii' the c.h I'o r-Ln e is then passed into a blackened bulb containing hydrogen gas, the ga~es· con:bine in complete. darkness. Such a reaction taking place thr9u~_!1.; the agency of light is" called a photochemical reaction.

The wav e Lc ng t.h of: the light is a s s'o'c.i a ted w i, th a' particular energy~

(c) Physical State

The rate of a r-e a c t Lo n is frequently affected by wh e t h e r- the

substances

a r-e in

solid state

or in solution9

ego

solid silver n~trate

. ,-.~'. -

"tv-hen mixed '1,Jithsolid; sodium c h Lo r-Ldo gives no reaction, but Ln is o Lu t s-"

\

ion the reaction is Lmm e d i.a t.e ,

"

(d) Concentr~tion

Concentration affects both reaction rate and position of equilibrium( for' a balanced r-e a c t Lo n };

(i) Effect on Reaction Rate

The higher the concentration the faster the reaction. In 1867, Guldberg a rrd ,1'Jagge suggestedtllat " -t h e r-a t o at wh i c h a chemical reactionis proceeding at any instant .is proportional to the active masses

of the r-e act Ln g substances at that instant II. By "a c t Lv o ma ss c s " He rio w,

use "molar concentrations".

We may regard an Ble~entary re~ction as aonci stage reaction.

In the'eleDe~tar~ reaction

A

+

+ D

Ra teo<; ~~! ~'J

or

,.1vhere k is tbe rate 'constant of the n:~action.·

v. .:

. -"---.

!Vlost reactions are not e Lernen-ta r-y , !"l,o!'Iever~~-th€y proceed in a series

... ;' .. -

of stages. Each stage has its o wri r at e of reaction. Oft'en one stage

occurs more slowly than the rest and the rate of .the. overa~l-r~~~tion

.- .. __ -."

is governed by the, :r',ate of"the slovle~t ~·tage-..;.'called the rate deter-

mining stage.

Ln.i marry complicated reactions (not elementary) the overall react~()n rate does not vary with molar concentrations of reactants in the way expected from Guldbergand Waage's rate law.

THE \'lAY IN \'JI-HCE THE RATE OF A REACTIOI';j DEPENDS Ul""ON THE VARIOUS

C01'JC~NTRATIONS CANt.JOT BE DEDUC2:D FROM 'TI1E EQ,JATION ~ IT h.UST BE OE.TAIN8~ ~ROM EXPERIM£NT.·

(ii). Effect- on Position of Equilibrium

The lavJ 'of' mass action states that in a rev;ersibler:eaction, there is a fixe~ r~lationshipat a given tempB~aturebetwee~ tbe molar conc'eht.ratrons of't1:.enrodu·cts' alia' those of the reactants in the equili bri urn mixture i.

The above is deduced from many

, .

experl.mentse

In the general balanced reaction~-

A·+ B'~ C + D

it is found experimentally that at equilibrium:-

Ii

,~ l~QI.[DJ .

L~II_BJ '

wh e r-e

[C]

is

'K is ,the eq~~a:Yiorium c'ori'stant(,"i,t~)ies =w i. th teI;'rpera t.u r-e ) •

-,''':

The law of mass action can be e xp r-e s s e es in .t h e most general form as.~-,',

pA + qB + rC

xD + yE + zF

K =

lbJ x' [EJ r [!J z [Aj p [BJ q [c] r

Concentrations in. gaseousr'eactions are sometimes expressed in terms

. : . .

of the partial pr~ssures of the g~ses.

Determinatio:p_of Eguil'ibrium Constants. (Eeys. Pg. 380) Liquid Systems --Esterification of_$th~nol

co rrc s _ in equilibrium mixture

(b-x)

v

x v

x v

tlatlmoles of ethanoic acio. are mixed withtlb"moles of ethanol.

t 1 1 ~. l- ._ 3

v = 0 ta vo ume OJ: rm x t u r-e a n Ii1 •

3s-

- x moles o~ eac~ have reacted at equilibrium.

6

K ~ _ @E3 C50~~Jl5], ~I20J [9E3CQ9.fJ EC2H5o~n;,·,

(xlv) (xlv)

...... t -:: ~ -,

:'-,'

.~:';''''.:'' ;:'-.;-.~!~~~ .. : .. .: ,.- .::..::.:..2~-.~·:?_~·_·,~:':.~ .... ~~-~~~ .cx: - ;~:. --:...':~; .. .: .' ~'--,",- ":'_'~;~"";""''''~ ..': ~ 2

-...~~ .. ~x~.':'.~: -:::-:"~' ±== '..

, . __ . _ .... _.-c ,~, ., .... _ ... _........ . .. ' '_'._.~; .. ,, __ ., .. :._'_- .. _

.. ,

- ' .. '

..... '

"''' ...

',_.: .::

(a-x)

(b-x)

.~ .

. _._".-.- .. ..-. --_ ... ~- .,

T~U.sl!'K.!'-. Co.J(\bCLdete;r'm:in~ fro._m;th'e·:·'C9mpO.sit'ion of. the equilibrium. mixture .• -;r:..,~, g{U\er',al. .eql,1i; ~b:r-iUJfr:"Con~t;al:lts -va~y: "ri~th temper:~E:.ure{as do" rate consta.ntf'). Rate c oz >t?-ntp a Lwa y s ilJ,'9XeaSe .. lith. Lri c r-e a-s i n.g t emp-,

e r a t.ur-e , ~~uil \brium.con~b-ants ma y decrease' or increase depending on ':!hether the... tuction is. e..)totr.ermic 'o r' e.n do.th e r-m i c , Equilibrium. constants (un1\ke rate cOl\stants) are !!.2..! a:ffepted by catalysts.

A known 2.1'f'()unt of acid and alcohol are put into a sealed tube. The

tube is ';JO- ~ed. until e q u i.L'i, b r-Lurn i:S·~:h:~a-e-h~·The-<E-ube is .. ti-i-en--bT&l~n~-;':~':' ~iid:6r.;:...wat-'e.f.:_iir~ .. tJ.Te::::be~ai.A-i.ng. -e:tha:hd i c'acid e~\~imiited by-u,tit-ra tion

wi th s tan;kd.SodiuQ···h.Y~:f-.()i.icJ9.L80 IOiTion.'::~~-i-n~phen.6-1.-pY.:t-ha:l·ein("'lhY''?+-- ~, indicat6.~t:_,,_llsj_l'..& .. th€>:::,v.~~v..:L:<-O':£",cX-;,f;o~~4~~K-i..i-,'·{}a~.iou-J:.a~·~ft'8;:'~b6~~·;·,i_',,· .~~.-;":<

... ~. :.~'t ''_. ..~ :._ ~~.

Hhe.n 8· 28g of' ethG\1101 were . treated ui t h 60g~"of~·e-thanoic--ac~d9.

- ;~t-~:~ .. ~:-~-.:; t-::;: ... -·~;1. .. 3:"~; .... _.- .:- .•.. c, '.:,' ",.

4~"74@ of acid reMained at equilibrium. Calculate the value.of .

. . ~ - ...

K.

ate c: u iIi i i urr 49 • 74

no. r:1oles~ or~thanoic aQi! =_ .60" - =-, 0.J349m9J,:e.s.,, ... n

Thus no. of moles of eth2Aoic'acid'reacted = (1-0..829) = Q.171moles. = no. of moles of' ethanol reacted. '" ~8

no. of mole...s cf ~i1h~Ll,o~ ::2: ~ .s t a r t -, =;: o~6 . ,,0.. 18 m~t- _

1L.et volume: of Mi-xture be V mj • '

Thus no. of nt()\.es of eth21\ol at equilibrium,= (0..18 - 0.171) = 0.009mol.

K =

@_::,COGC21i§j TB~J' f9H3COo-f© §2RSOHl

=

. ..

ego (ii L Vhat: mass of et\.·wl cthanoate should be p r-e s en t in the equil-

_ ,:o.-~ .:..._._.__.: .. _ ..... ._,

ibrj-lm mixture formed from 13.Gg ethanol and12g ~thanoic

a..ci~.

(;...8~t 0( '~be~no. o f'<mo Le s of et'b y L' et.h an o a tee = no. of'! mo Le s'<o'f : ""a.te-\"" ) at equil{.brium. No «: of moles of ethyletha~oa,.te formed ::: no, of moles of e t ha no ic a c Ld i or e t ha.n o L) thcit' have reacted .. Using the value of I{ p r-e v i o u s Ly , c a Lc u La t e ds»

. ~'- - -. ~ .•. -.~-_ ' .. -_ :'__'__:._-' .. ! . .'. ~~-.-.:.- ~ .. ;':.~:' _,- .. - ---:.,.._.-.;.~ .. :.;._~.:..::....:. .;.:.._--...: -.. '" .--- .-.-" ._ .. _ .

=

..

. -- .... -_ .. _

.. ' .

: :;)

36

-

1

2

= x

••• 2.92x2 - 1.96x + 0.2Jj = 0

Solvini ~~. for ax2 + bx + c

:' !

x = 0.158 or than the EO.

005'14. The tat t er v'a Lu e i s rio t pos sible as it is g-rea ter cf ~oles of ethanoic acid pr ethanol at the start.

13.8

-. ~ moleS = 0.3 moles

13.8g e t.ha no L

. 12 l' 0-2'

12g e t.h.a.n.o i.c r.c i d = 60 me es = . ~

moles. '

Thus mass of ethyl ethan.o[~tE\,formed = (0.158 x '88»)5 =

·f· ...

Gaseous S_ys_:;;errts, ,

Here the equil~brium constant can be expressed in two ways.

Concent.Ia~_ion Equ;Llibr,iumCons'tant. (I\.c) . -- if obtained from concentrations of subEtances.

(ii) Pressure £c;u±I'ibriUD Constant (K ) -- if obtained f'rompartial

_ --..r.-,.. .. ~. p

.. " - ~

pressures c f gases p r c s en t , This' Is'<5rt"en-'l1lOre' -c o rrv e n Le nt in

{ . )

\ 1

.gas., .. e o u s ~ea.ctions. K arid I~ may? or may not be eq ua Lv

,(; : P

·(T:.rlen there -i,s' Ib chang-ein' the' 'iota'l no. o f' molesr<_: . - K·

c - -p •.

lilien there is a change in the total no. of moles

K does n6t = K •

c P

Determination o~ Reaction ~ate

The kno~ledge gained from a study of reaction rates can be used

to adjust reaction conditions to greatest~dvantage. It also provides Lnf o r-ma t Lo n a b o u t. tb.er:1echo.nism of a reaction. The 'jay in whi.c h. the

rate of a reection varies with tEe concentration of reacting substan-

ces ,is d erro t e d by the O:A.D!~ of the r-e a c t Lo n ,

ego ECOOC?-I-i5 ethy_';_ methanoate

Ee.OOH

TI1C: thano ic acid'

. ., ..

the rate is proportional to t~e fir~tiPower of the concentration of a

:', .

single substance.

ie.

-d [~COOC2H5J dt

=

k1 = rate constant.

Second Order 2eactions

Consider the reaction~-

- <, 2RI

+ 1.2'- d

The rate

of disappearance of

or

is

=

=

::

dt

dt

" '!"

<t.:- "t, ;,,'

The rate of the above reaction is first order with respect to hyqrogen"

'.- '.~. _ .. ' "

:first order -;~:.rith respect to iodine, the overall reaction being second

>.

order.

In the Seneral Case

and their conc~ntrations areg-

__ ..:... '". 0.,. _. _._:

[1] ~ [B] 9 [c},{Dl, e t c,

s e'pe.r-a t.e Ly. proportional to CAJ a 9 [BJ b

If the rate of the reaction is

etc»

and the k Lri e t Lc order of the reaction = a '*' h· + c. + d etc G

But the order of a reaction is not .. al~!ays·the·saille as the total no. ' of

~oles taki~g p~rt as repre~ented by the e1uation •

. ~ ~ - ""-.

The kinetic order does agree ,:/i th the no G of E101es of reactants' in. the e q.u a tJ,,on in some case s-- thes'e ar:e, usually elementary (ohe-s:t e p ) reactions, In rao s t c as e s there is .n.o agreement.

CO:lsi der cre ~~e..composi tion of l-::.ydro_g_en p~ro]:ide.

This

reaction is

found to be

first,

not

second order,

the r e a c t Lo n do es - nc:t take plac e simply by' tHO moLe c u Le s of - I'1y-d~ogen. peroxide 6ollid~ng together.

-d[H20~ dt

=

A pos~ible reaction 8echanism from the above facts is:-

fast

Nany second order reactions b e c orn e first order when one of the reagents is in excess--- such a reaction is called a "pseudo first order" reactio:l.

First Order Reactions--

. '.

_,- ......

A~ B -:- C -------- first order elementary r-e a ct fo n .• ,

let initial c ozre., of "At! be "a" molm-3

let "x" mol ha-..re disappeared after time "til

then?

dx = k(a-x) dt

k ~ rate constarit

-In(a-x) _ .. k t -I- c, WOlen t = 09X = 09, •• c = -In a

-In(a-x) .. kt - ln k = ~. In L_:_~) ~ .'

't. \ a=-x .. •

'0 kt ~ In a - In(a-x) k = 2.303 10g1o{-§:--)

t. I a-~

'-------~-...,.!..,.~~

units

.. o· •

a, "

In the above, because concentrations are involved as a rati09 the

actual concentrations need not be f'o uncl-o-w e need o n Ly the ratio

so relative val~es of pressures will doi~stead of comcentrations~

Fen a first order reaction ~hetime fOT_a,given ~,of ~ given substance .. t~_c?_....2~_?-nge (or <:l~.c~) -:h.? independent o f' _tJi~J tial con~entration.

For a ~irst order rea~tion the rate constant is the fraction of

the molecules WIlich change in unit

..L.. ."

c a.m e ,

Thus i~Q th8 reaction A~B -{:C\' t':.h.e time. tl for halfcif A to

-3 -3

disappear is -the same ,Jhe'~her vr e start w i t h lmol D. or' 2L1Ol ill •

In both c a s e e s >-

=

.2.303 log,,,, l·u

k

a

2.303 10g1 02

lr ~.,._

a a';' 2

= 9,,693 k

= half-life for radioactive decay.

Radiocarbol"'.. Da.:ting

14C is created continu~ll~ in the atmosphere by bombardment of' carbon

. !' . A L '

dioxide by c o sc i.c rays", The resul ti:ng I ~G' becomes evenly distributed

throughout the atmosphere, oceans9 'ati~'all liVin~ things 9 a constant

t' i .. . t.a i ',' 14c .. l i t. ,.. ,. ']"f: 12C

ra 10 belng melD a~nea oe~ween a~d 1 s als1ntegra~10n proGuc. •

-('Then plants ani animals die 9 r e n.ewa L of their radiocarbon ceases, and

14 ".

the 'C present d e ccay s at a known rate. The age of the specimen can be

14C•

found by measuring the radioactivity of the remaining This is

reliable ~or a~es up to about 30,000 years.

To Sho\! a _;_:';_eaction is First Order. _ Hess Pg. 37l.j-,

Consider the reaction 2H202 ~ 2fI20 .; 02 '.

At intervals withdraw 10cm3 and ti~rate with standard potassium manganate/Vll) solution.

At t#:me to At time t-,

let

titre be V (D

let titre be "1

. . . .

._ •• after time

't , 9 I

disappeared9

ie:

x~ can be repPes-

ented as (Va - V,); a-x can be repres~rited as V1 • He~ce for different values of t we can-work out the cori~sp6nding values of ~O-Vl ~e. i-

ano. of

V 1

j~~2. a-xo

From this data there are three ways of s h o w i.n g the r-ea c b i.o n is a f'Lr s t

order reactiollo

(i) Calculation of t~e rate constant

= 2.30] log1 u~ k t

a

J __ wo r-k, out

for different values of time and find

a-x

they are constant ino.icating a first order

reaction.

Graphical evaluatiohoi~rate

"

constant

-;

llearrange tl'.e first order r a te -equ2. tLo ri a"si..:

-~- - --"" t ~'-;-- \

,-Tog ";-a-x 'f , 10\- --,

=

k

= a c o n s t a nt ,

. ' .. ~

2.303

-"--

L· ..

.#1.

I \

PI t - I a \i

o '.Log ,---~ - ','

10 \a-x J

- >

v~. t -- a straight line gr~ph indicates a £irst

order reaction~ slope or gradient = k/2.]03 !

(iii) _' 1-;:al f'-li:fe method,

P'I o t x agains t t., From t,--: a graph find the time for tl,-e ini tial c o n c ,

of H202 to be reduced to l"-alf that value, tl-:en the t.Lmc for it to be reduced to {- the value etc. These times \ViII be the same' for' a Iirst

order reactioL

Second Order Reactions

A second order elementary reaction can be represented as:-

A+E-7C-:-D

Let the initial conc.

-~ of' A and B be"a" mol m J.

Let Ox" mol of A have disap})ear,edaftert,ir::.e t. Ra te =k [A] [ED i e. aft er time t. , dx = k (a-x) 2 dt

1 1

regrranging and integrating~-

• c·

dx

(a_x)'2 .

=

kdt

.e. k-t _

x

9 •• k =t 0 a ( a':"~

x

a{a-x)

Units

of k =

c o n e.,

x time

-1

= conc.

-1 . time' 9

3 -1

ill mol

-1 $

conc.

Here, the time,t/,fo~ half the reaction to be completed, i~ given by:~

1

1

.' ieotl is inversely proportional 'to -t lre .

.- k a

initial conce~trntion (cf. first order reQction)~

To Show a ~eactionis.8econd Order.

The same three methods as for a first order reaction are used'; {i) Calcu~ati~~,of the rate constant

Find x for various values o? t and calculatek from thesecond.order rate equation. The v c.Lu e c of k "rill be the s anie for 2.. second order

reaction. ('~. \

\Ll} Grap~ica~ method

.,., , .- .. - .

',;

' .. ~ '- ...

.:~

x

=

tk

• ,plot a(a-x)

VB. t -- a straight line indicates a

a(a-x)

second 'order Y'eaction9 kis 'fhG -gr2_dient.

{iii) Hal:f-'lif.~_Elethod

Plo'~"x ;_~Qi~st 't, a; x tl should be constant for a s;;;cond order reaction.

(8) Cataly.stsJjeys Fg. 363

A catalyst is define~ as a substance which alters ~he speed or

rate of a reaction but renains the same in mass at 'the end of' the

reaction or at equilibrium.

hOn1(jgeneous I

Catal,sts /

\:Jhen the catalyst and the,reacting substEi.b.~es are in the same physical stat6~-

\

~eterogeneous - when i~e cat~lyst and the reac~irig substances

are in diffe~ent physical state~~

"

.r ,

Gener2.1 P:r:-oper-cies of Cat2:.lysts

12

Unchanged in Blass at the end'ol t~ereaction(or at equilibrium) Al ter reaction rate but never t>e final posi tio_n o:(_::_e.quilibrium A. small amount: o f: ci-ta....lys't''' iu'fluences 12.rg'e- 'amounts "of reacting

. "

&tlhstances

l<-) .(re u s ua Ld.y= e p e c Lf Lc Ln character

1) 2)

J)

5) The effi_ciency is_ .o f ten, increased or~'dec-r-ea-s'ed -b y traces of' other

substances, Tne efficiency' is Lri c r e a s e d by a p r-omo t c r , ego in tho -HabBT?rOCeSs aluminium oxide is a promoteri'or the irari catalyst. The ef:ficieiTc~l is d e cr-e a s e d by a n inhibi t.o r'{ c a t a Lys f p o Ls o n ] ego

TT S ncn

'"2 ;: tJ. 1,.

Autoc8.taly,sis

This is V!hen one of' t2e p r-o du c t s of a r-e a c t Lo n acts as a catalyst

for that ~eactton, ego in the oxidation of ethanedioic ~cid by potassium Ll2.ngal'late (VII)? tne m~hg~n:ese(il) sul:phat~(VI) produced acts as a catalyst and s~ the re2.ction speeds up.

j3;xpI an8. tio_~ of Ca t8.lyti c Lct~On

CatalyticacJcion depends upo n the Lo wo r-Lrrg of a c t.Lv a t Lo n energy. This may be ac~ieved in tWOW2YS9 6hiracteristic o~ homogeneous ot hetero-

geneous catalysts.

homogeneous C~t~lysis

This :i_s ucu2.lly expls.ined,oy tb.e:~interriediQt·e cO~.'fJ<?u~c. -:theory.

H~re the c~talyst takes 2. definite p~rt in the reaction by forcing 8.n

intermedinte compound which is subsequently reconverted t6 t~e product

,

regenerating t~e cat2.lyst9 ego in the lead chamber proqess~

theoxid-

- . _."

ation of' SC2 t~ SOJ is catalysed by nitrogen rionoz~de(nitric oxide). The La t t e r- acts as an"oxygen' carrier"'.

2NO + 02 --> 2r-T02

N02 + S02 -i",SO':) + NO

, J

S03 + !-.L20 -), H2-50'-l-

HeterogGn~~us Catalysis

"

This usually c~epends on as!,sorption.

Consider platinuD atoDs 2t the surface of some platin~m as having

"free v a Leri c Le s !", The larger the surface a r e a , tl:e more "free' v a Le n o i e e "

for a g i.v or, EJ2.SS of platinum. These flfree ve.Lcn c i e s " are able to attach

a t.orns o f' 0 tr:_er substances to the s u r-f a c e. Thus 'ltJhen p La 't Lrrurn c e, talys as

the combination of hydrogen and iodine vapo~r'it i5" supposed that the bonds b e t.o o e n t,he hyc1rogc~l"" 6. toms arid the iodine a tons are broken and

..

the atoms are adsorbed OLtO the surface of the platinum.

4-2.

-

If atoms of hydrogen and iodine occupy adjacent positions9 an activa-

ted co~plex of the foro

II -T

!

1:

I _opt --- Pt-- Pt --pt ---

j i I I

-pt - Ft --_ Ft - Pt

l l I

is forDed.

The complex c o n s i.s t s of: a hydrogen atom and an iodine a t orn joined to

each 0 ther a~'lC_ to p Le .. t.Lrrur: a toms by a brro r-raa Ll.y long 9 vIeaK bonds 0 The

activated cOL~lex has only a fleeting existence. Provi~ing the hydrogen

and iodine ato~s have sufficient energy the bond between them shortens,

the bonds wit~ the platinum are broken, and tte newly ~ormed molecule

of hydrogen iodide vapori~es9 leaving vacant sites for t~e adsorption

of furt~er ~tODS.

(f) Pressur~

Pressure affects only reastions in which gases are involved.

(i) Effect o~ Reaction Rate

An inc~ease in pressu~e on a gaseous system is equivalent to an

increase i~ concentration. Thus the reaction rate increases for an

increase ~n pressure.

{ L L \ -",,<'-""e c -i~. J w~.L _ v

on ~osition of Equilibrium

If there is no voluDe ch2~ge there is no effect on the position of

equilibrium. If there is n volume chango, t~e position of equilibrium

c h arrg c s a c c o r-c i.rrg to Le C":& t eli cr 1 s p r-Ln c i.p Le ,

HcterogeEeQUB 3ystc~s

These are syster;:s vIi-lere the d i ff o r-e n t substances are n o t 0.11 in t[-lG

same physical 3tate, ego CaCOJ_ CaO + CO2

"',__~-- • A solid b ob a v e s in a

reversible ~e2ct7on as i~ it had ~, constant concentration. Applying

the lay o£ GaGS action to the above reaotion:-

l(c'" i~a~ [C02J [caCOC)J

--'

as the concentrations of CaO and CaCOJ during the reaotion reoain constant9

:Kc;:: C [C02] C2

thus the conoentration or pressure of CO2 is constant for a pc r t Lcu La r- tecperature. The

value of this pressure at a given temperature

is called the dissociation pressure at that

ter:-,pora t.u r e ,

Eel U\ J...\ Q,R IR

y

..

,-

!\. \ t

.:}_,,, ...... ._ ) 3. CJ)).\J

L'. l. \..\".~

~

\.}~.~.

~~ c..~

~. ~\)~~~.

M~'Qco'N'.~~"- ~Vf't~~ sv.it~ ~ ~~ "'\.._~'" OIf\C...

1'2.0 too

1.0

~ s t'j'
I
I f
I rC c
f ( 1
I (
I ( i)'
/ ( 1)
I ( j
I I
I ( f
I I I
t ~
I ( ( f ~I
i:
I I t -:
I
- ,
. . '.

'Vttf ~~.

(rJ~'t}

A

~_ ~ l-h.D 3H~C H'lO Co __ ':;OS~

"" " ._.' _.. .:

D

~ . R

~o -----r---------

I I

t ~- 1\J ~ c.Q.

R' {

or--- _ _;I

-lO~O----------------~--------~---

I c 10: ~:S#& rc 4-0

-sc

'83

I (

( I c( ( !

• I ~

V. \ _ \\ .~;-- \. -,

I,_).,.-v\- - ~ .,..,..".. X •. .\ . .u. \~~

· .' - '.' - :'.". -_' ..

4lOt r-~-' --~ ,So\~ ~V\

ft l\~~'

Y- ---.~-- ..... ._..._,--._..

~ ~\~X. ~,"'- +

"~~'

" O{~a

, \OI\,OI~~ •. lOoo{o Cl

, y, 1.0 1;,"':' , , 0 0 to ~ '1\

-A~ C =;~.~eo..t .... ~I.L_ s~o.J: t.~~ ""'~ "-\..Q. c.v-o.y~<"\

,~~t£~a.-&_~,"=~~s~ ~~ t~~ Sa.MQ.,. \

" RC'~'~, ~ C~~~ (a;.~~ t:~, ~ ~,~~~l.\

'Dc.,~ -~~,',~u..~ C~~ t\~,o.l\'~ s~~ ')

~ \:\'<a. 'G..u~ CuS~ \;"'"-~ ~ 0. ~J::";..~ ~ Sd~~';' i\'\;_:'_k

i"-'Q;. ~~~ ~ f\_2*c, 0.. C-~ c..a",,~~~ \c..;_~ J:o,

~~ ~~ o.",\. <:.c..-.~os~'\io" \J~~ ~\.~ ~~u.~',

So\~~~~ .. + l\\~,~

Sl~fo ~~ 84l,1, l'

/

fO.w1 ~

.. v to ~'I\

. 0 '[0 -tAct.

...;)

.' '.

._

-{\..q, - moi4 2 ~ c., .... ~ ~~ ~¥\ 'l;. ~ oJ:: ~...:...t =-. ' "." ~\:h~ ~~ ~~ ~,(\l\.~ k'<:""-~ C8 ..... ~ M""9:.,,,~. ~ iD. ~~ cw..~ .w..x. \I..~ ..r t", + ~'" ~ <:<1_ ~."-,,,3. 1"''7,.'1:. ".,_ .

\\

, -,(\",,-=- . ~<>-'!:..~~ ~""- ~ -. s\"o~ 1;:\-<1.. Q._y_.J::,~,-,,-, 0&

s~ ~.) Q.L.Llcu:..~~ I :_~ ~V<A~~. \ .

~~ t-o~ M.~~\.'M.U~ ~~~'-O..A t'-"_J ~\",Q_ c..D"",~.~~_,i.

M~ ~y\... V> M\: ~ s.1.:-.._~~. F\ s" e, ~ ~.::. ;_,,)~,.0> 0.. c>,': K

s~~ Cb""'~~.

_~. ?~U,.), o..~ (. ~d l' e. N>.3;"

-\ocotoB

/

_-

....

....

" '\

----~

(\0)

\J ~""" ~~' ~ \:-\" ~ S 0\" , ""o.>.~ ~ \,.._ 0... {<'.a. ;<.', "" ..... N\ (~O s'. t~ ~ 'j C :Ji.':"" .; ~H\. K~c\'\"'\ 't\ ~~\..,) ~

\J~ <z.:.J: 0~~ ":',"'" ~~,~<Y'~~."

C.o ~ ~~L,~,-\ J ~\A.q_

, ..

So.- 'c~o...-\c ,-": al..;) ~--

/00 ~

lOO:

-~s .

I I I

O~--~~'O~.~~·------------~~

~ 100

0(0: ~ ~<:.~

~. .; c.o-M: ~,~ ~«.o...~#\ . ~ W~\..~" o.~c\. ~ Wo.~.

, t

,

,

I ,

I

o c 0

'\ ''''~

ton .

%0 o·

so

'~ ....

rse : 160 144····

100 .

~o 60

~.~----------------~-

t), la 'l..0 30 ~ SO 60 ;0 se 9,0

°10 ~ ~~Q..

I

Ccv0.u._~~ ~. \:,~ .);-0. ~ ~. """~ "';.& e, ~~~

~ ~~~ C4}~~~. \.:JQ... ~ !\.\-~l. ~~ Icc ~I~~~~~ ~~"\~ ~ ~~\..._ ~\;~~ '~- ~~. \)~- ~.~~~. G '<\.._~ I::;n\,,&. ~ ~tt.oo"'~. ",,\,_Q.. \:.\:.1 I;~- ~"'Jl<)U . ."L. ~ ~- ~~",-,- \:~ '0""(<!V.\' ~~~ ~ q):.~ ~ ot' ,~~ ~ I::"""~ '\;:..:,(l. ~~~ 1 s."~,,:, &;..,~ ........ ~ ~. '" "L (J:r. ~'" ~- i:""~

c\O~,.~_ ~ ~ ;r-.........u~ ~ c:>..l'r\....n~ ~ oS ~ "~\.)o...n. ~~.l. ~\Q...,

~.

~t.. ~ \.o~.· ~ CS~.

~. \ ~~Q.. :,._. ~~O

-

-

t 62. 1

I Electri·c·al Properties of Solutions -

k electrolyte is a substance which conducts electricity when dissolved or molten.

ElectroLysis is the conduction. of electric:i ty by an electrolyte. This type of conduction differs from metallic conduction as below:-

1) In electrolysis, chemical changes occur at the electrodes.

In metallic conduction there are no chemical changes.

~) An electrolyte conducts electricity more readily at a higher temperature.

A metal conducts electricity less readily at a higher temperature.

3) Ions move throughout the elec.trolyte.

Electrons move throughout the metal.

Faraday's Laws

In 1833 Faraday summarizeC!-· his--ex:p.erimenta1. results in his laws of elec.:-trolysis.

1) The mass(m) of substance dissolved or liberated in electrolysis is directly proportional to the quantity of electricity which passes through the electrolyte.

m; = eIt

~ is the current in amps. t is the time in seconds.

e is a constant called the electrochemical eguivalent. The electrochemical equivalent is the mass of material liberated by 1 coulomb (1 amp for 1 sec.ond) of electricity.

2). The masses of diff.-erent.. products set free: by passing the same quantity of electricity through different electrolytes are directly propor-, tional to their chemical equivalents.

-

-

whereM.,andlV\2. are the:; masses liberated by the same quantity- of elec:tric.it:w from substances with chemical equivalents £ I and. f 1.. Thus the gram ... equivalent of any product is liberated by the same q'ua .. n:tit'T of elec:triC±ty-o Thi.s quantity of electricit:y,:- is 96,487 coulombs and is known as the Faraday. These ~a~~ are obeyed exactly over a very wide range of temperature, concentration, and current.

Y is the charge on 1 mole of electrons. F is the quantity of electricity to liberate one gram-equivalent = 1 mole of univalent species.

Thus F divided by the charge on an electron = the number of atoms in a mole ie. Avogadro's no.

:::.

,\64-87-

\. 602 x lO -\,\

-\ Mol

\- , ~o

. .

t c:

~ is found by Millikan's experiment.

Ohm's Law

Experiment shows that at a constant temperature the current flowing through a conductor (metallic or electrolytic) is directly proportional to the P.D. applied across its ends.

The ratio of P.D. to current is the Resistance of the- conductor. The uni t of resistance) is the, ohm. ..J)_.

A conductor has a resistance of 1 ohm when it allows a current of 1 amp a

so

to pass through when subjected to a P.D. of 1 volt.

At constant temperature,

t - length:

A _ cross-sectional area

f '::' resistivity (rho). (Constant for a given s ub s t an c e ) ,

f is the resistance between two opposite faces of a unit cube.

(~ is then uni ty.)

Conductjyjty

Irr electrochemistry we: prefer to use the conductivity rather than resis-

tivity. This is the reciprocal of resistivity and is defined as the con-

~uctance of a 1 cm , cube of the substance or solution. l
'Conducti vi ty - \<'(kappa) -\ -\ k - -
is usuall.y expressed in _n..;. ct1\, - P
C - k t c ::.: c:ondUctanca
k ~ -I -,
- hence units ~ eM.
- R The conductivity of an electrolyte depends upon its nature and also on its concentration. The typic.al way K varies with concentration is shown below:-

conductivity

c,onc en tra tion

Measurement of: Conductivity

This is normally carried out by the Kohlrausch method which uses the WHeatstone bridge circuit below:-

Conductance

(resistance (\. )

A

~-----------~----------~

oscillator

variable resistance

glass supports

electrolyte:

Conductance Cell

The resistance of a cell containing the electrolyte is compared to a known but variable resistance \\" ' The spacing apart of the electrodes is constant.

~§ -4

-

Alternating current from a valve oscillator or induction coil is used

( about 1000Hz ) to av.oid polarization effects (ie. changes in the resistance of the cell' due to formation of gas bubbles on the surface of the electrodes as a result of electrolysis). The null position is indicated by minimum sound in the headphones which are connected to a valve amplifier to increase their sensitivity. The sharpness of minimum sound is usually

increased by connecting a small variable condenser in parallel with the
post offfice box~~o balance the capacity of the cell.
A t minimum ~l AS R, AS R:l,
.- $0 x )
(\2- ~c J \1c . where.~C is a wire of uniform resistance and S is a sliding contact .. Several values o:f ~t are :found and the average taken.

The experiment is then repeated with a salt solution (eg. KGl) of known concentration to find the cell constant (ie. a factor emoodying the physical dimensions and spacing of the electrodes in the cell which rel~ ates the resistance of th'e cell to the conduct.ivity of the electrolyte) .. Throughout the experiment the temperature o:f the electrolyte must be kept constant. Also conductivity water must be used.

Molar Conductance

This is the conductance of a solution between two electrodes one centimetre apart which enclose one mole of the electrolyte between them. I:t is denoted by'" .' Since the conductivity, k , is the conductance of 1 em~': of' solution between electrodes one centimetre apart, it :follows that:-

/\

kV

where V is the volume in cm; containi~g one mole o:f electrolyte. 1\ is not: measured directly but is determined :from k using the. above relationship .. The molar conductance of a solution. of any electrolyte depends upon

temp~rature and concentration.

Variation o:f Molar Conductance with Concentration

The two general ways in which the molar conductanc~ varies with concentration are shown below, where 1\ is plotited against dilution. The dilution is the volume o:f solution in dm~ which contains one mole' of' solute.

66

-

\ ao I
\00
80
6O
4-0
1.0
0 Soo \000 \ 500

Curv.e A- is typical of most salts, aca , H~S04' HNQ3' NaOff, KOH. In these cases the conductance is always high and increases only slightly on diluti on, soon _r eaching__a . .maxdmum.oza.Lu.e, knO_WIl .. as. _ th.e.;.moJ:ar. _c:ondu c.tanc..e:.,;:..a:t..._. __ .. _.~>~ infini te dilution and denoted by A 00. Substances whose molar c o.ndu c t an c.e varies in this way are known as strong electrolytes.

Curve B; is typical of most organic acids, NH40H, and certain mercury sal.ts. In concentrated solutions the molar conductance is very low but it increases steadily with dilution. Substances of this type are known as ~ electrolytes. There is no sharp distinction between strong and weak elec~ trolytes: some are of intermediate character.

The importance of molar conductance is that its variation with conc-

entration faithfully portrays the variation in the conducting power of

the electrolyte since the quantity of electrolyte between the electrodes remains the same whatever the dilution. This is because on dilution, the volume of solution taken changes so that one mole of electrolyte is always present. This is not so with conductivity where the variation with concentration represents the resultant of two different changes: one in the conducting ability of the electrolyte and the other in the quantity of electrolyte contained in the cm? of solution between the two electrodes. Thus changes caused by dilution im the effectiveness of an electrolyte as a conductor of electricity are obscured in the case of conductivity, ~ •

For a strong electrolyte, molar conductance at infinite dilution is best determined by plotting the molar conductance against square root

of concentration. For very dilute solutions this gives a straight line(see graph below) which can then be extrapolated t.o cut the axis, the intercept being taken as A QO •

6:

Weak electrolytes also have a characteristic value for molar conductance: at infinite dilution, but in their case it cannot be determined directly because the graph is not a straight line. It is calculated by applying Kohlrausch's law of independent migration of ions.

-:

Variation of Holar Conductance with Square Root of Concentration

The Simple Ionic Theory

During the nineteenth century numerous attempts were made to explain the previous experimental facts. The most notable of these was the theory of electrolytic dissociation, generally known as the ionic theory. This was put forward by Arrhenius between 1883 and 1887. The theory postulates

that in solution all electrolytes are spontaneously dissociated to some extent into .positive and negative ions {or radicals).These ions have completely different properties from-the atoms from which they are derived. The dissociation of an electrolyte into ions in solution is regarded as a reversible process, the extent of dissociation depending upon the nature of the electrolyte, concentration of the solution, and temperature.

Arrhenius explained the variation in molar conductance with dilution by proposing that in a solution of a strong electrolyte the proportion dissociated is high at all concentrations and increases when the dilution is increased, soon reaching a maximum value when the dissociation is complete.

He suggested that for a weak electrolyte the proportion which is dissociated in a solution of ordinary concentration is very small but that this proportion increases steadily with dilution so that the electrolyte is completely dissociated at infinite dilution.

Electrolytic conduction is explained by movement of the dissociated ions through the solution. According to Arrhenius's theory the amount of product liberated at the electrodes during electrolysis is proportional to the number of ions discharged per second and to the time ie. to the

1-- ,... 1-:0' _ .... __ .... ~ .... __ _ -t:" _., ~ _ ..L.. _ ~ _ ~ 1_

S·imilarly the masses of different pr-o duc t s liberated by a given amount of electricity are related to their chemical equivalents because the masses of the different ions per unit of charge are proportional to their equiv= alent weights.

Arrhenius explained why electrolytic conduction obeyed Ohm's law by proposing that an electrolyte partially dissociates as soon as it dissolves. Thus ions are present in the solution all the time( even before the pot= ential difference is applied) and no electrical energy is consumed in ionising the solute. Thus the dissociated ions move towards the electro= des and are discharged at a rate proportional to the attractive force acting upon them as a result of the applied potential difference.

The Arrhenius theory also explains why solutions of electrolytes

exert higher osmotic pressures, give larger freezing point depressions

and boiling point elevations than expected from their relative molecular mass because they are dissociated. The abnormalities were used by Arrhenius;

~. and va:n~,':.f Ho:ff'';'<to<'''"e·al'ctr1:ai:fe··:-the~'''ext;e-nt'~of; ·ct±.ss6"c±at::ron-;.~,_--":,,.~~- -:"- "" ~-' . <-,.<

One of the achievements of Arrhenius's theory is the simple explana=

_~ __ :tion.it __ of'.f'-ers. __ .f.o.r .... common_._pr.o.pert.ies._sh.o.wn_._b.y. __ .aimp.l.er.......c.o_m.po.und.a._i_e ...al.L~ .. _

copper (11) salts show 'similar properties due' to "Cu+:!"_- ·ions.-----

Arrhenius realised that the properties of all electrolytes - as far as their dilute solutions are concerned - are the same as the properties of the dissociated ions which they contain. Kohlrausch hadaJ.r_eady __ shown this to be true for conductance.

The simple ionic theory can be used to explain many experimental observations ie. hydrolysis of salts, common - ion effect, precipitation, action of indicators etc. Indirectly they provide confirmation of the existence of ions.

The most powerful evidence for ·tbe ionic theory came in the twentieth century as a ,result of X-ray analysis of solids- many salts are composed solely of ions in the solid state.

The Degree of Dissociation

The proportion of an electrolyte which is dissociated into ions in any given solution is known as the degree of dissociation, ~'It is expressed as a decimal or as a percentage. Arrhenius proposed that since all electrolytes are completely dissociated ~t infinite dilution, the degree of dissociation at any dilution is given by the ratio of its equivalent conductance at that dilution to its equivalent conductance at infinite dilu-

tion, ie.

0(:::.

A

-

/\00

.£i-

About the same time, van't Hoff suggested the term £ (kno,nl as the van't

Hoff factor) to relate observed colligative value to the value calculated

.8 .

on the basis of no dissociation.

Thus i ==

observed osmotic pressure

calculated osmotic pressure

==

observed freezing point depression calculated freezing point depression

==

observed boiling point elevation calculated boiling point elevation

and lTV = iRT

for a given solution.

" -»

0;

o

Consider an electrolyte each molecule of which dissociates into n ionsv and let C>C be the degree of dissociation.

Thus

l - oC.

Therefore total number of particles present = \ + (1'\- \) 0( to only 1 if no dissociation •

,compared

, .

\

Arrhenius used this deduction to calculate the degree of dissociation of varius electrolytes at particular concentrations from the colligative properties of their solutions, and compared the values of ac so obtained

"

with those from measurements of equivalent conductance.In.most cases there

was good agreement for the two values ofo(, doing much to strengthen the confidence in the ionic theory.

Kohlrausch's Law of Independent Migration of Ions

In 1876 Kohlrausch noticed that pairs of sodium and potassium salts with the same anion' showed a constant difference \~\~. C('l'\~ rt'-or') in molar conductance at infinite dilution. There were similar results for other pairs of salts with a c.ommon anion or cation. Kohlrausch concluded that at infinite dilution each ion shows a charact.eristic conductance which is independent of the other ions present in the solution.

Thus the molar conductance at infinite dilution for any elec:trolyte equals the sum of the molar conductances of its anion and cation at infinite .dilution.

+

A-

This law can be used to calculate molar conductances at infinite dilution (ie. for weak electrolytes which cannot be obtained by extrapolation) provided the values for three suitable strong electrolytes are known.

eg. Calculate the molar conductance at infinite dilution of CHJCOOH at 2SoC, given that at that temperature the molar conductances at infinite dilution

-,~ ,-'

of HCI, NaCI, CHJCOONa are 426, 126_, 91 _n.: eM fC"O respectively.

I\CH3COOH - 1\ CH,3COO- + 1\ \1 +
-
1\ H c.\ - AH+ + !\ ct-
1\ i\)t\C\ - I\rv;o.* + I\C\- Modern:, Ionic Theories

Iri:histheory o~ electrolytic dissociation, Arrhenius proposed that the degree of dissociation of an electrolyte at any dilution was equal to the ratio of its molar conductance at that dilution to its molar conduct~ ance at' infinite dilution, ie. o.c = 1'//\ QO

When the degree-of dissociation of a strong electrolyte is calculated in this way, the electrolyte is found rio't; to obey Ostwald's dilution law(see later).Several other pieces of experimental evidence weigh against the Arrhenius theory as it applies to strong electrolytes. Studies of absorption spectra show no evidence of undissociated molecules in solutions of salts, and heats of neutralization of strong acids and bases are so concordant that they suggest, contrary to Arrhenius's theory, that all these electrolytes are dissociated to exactly the same extent in solution and this extent does not depend upon their concentrations.

These findings have necessitated an important modification to the original Arrhenius theory as far as strong electrolytes are concerned. In relating the degree of dissociation to the ratio of molar conductivities~ Arrhenius made the assumption that the number of ions present in solution was the only variable. This view is now no longer accepted and strong electrolytes are now regarded as being completely dissociated into ions in aqueous solutions at all dilutions~

· .lQ

The variation in their conductance and colligative effects on dilution Ls attributed solely, therefore, to changes in the velocities of their ions

as a result of interionic attraction, and the ratio 1\;1/\ ~, now known

as the conductance ratio or apparent degree of dissociation, is really a measure of the way in which the velocities of ions from strong electrolytes change with concentration.

"'

The modern view devised by Debye and Huckel in 1923 and developed by

Onsager in 1927, is that in a concentrated solution of a strong electrolyte, each ion is surrounded by an atmosphere of oppositely charged ions.

o

9 e

e

eg.

e e

e

e

no electric field - symmetrical

under potential gradient - asymmetrical

-

D±agrams to Illustrate Ionic Atmosphere

So the more concentrated is the solution, the greater the retarding effect of interionic attraction.

For weak electrolytes, interionic attraction is slight since the C011=' centration of ions is never large therefore the velocity does not change much with dilutiono Thus only a small error is incurred in taking the conductance ratio as the degree of dissdciation for weak electrolytes and in general the Arrhenius theory accounts satisfactorily for their behaviour.

Modern Ideas on Acids and Bases

In 1923 Bronsted and Lowry put forward independently the definitio~ of an acid as any substance which donates protons to other substances~ Similarly a base is defined as any substance which acts as a proton acceptor. Thus acids and bases are related as:-

acid ~ H+ +. base

"< _

These are preferred to the narrower definitions ie. an acid yields ff+ ions, a base yields OH- ions, b e c au s e, they also apply to non-aqueous solvents

and account for the way in which the 'strength of an acid varies with the nature of the solvent.

Ii

The views of Bronsted and Lowry have been extended by Lewis who has

defined a base asa substance possessing a lone pair of electrons capable of being used- to link it to another atom, and an acid as a substance

1

wj:~ling, to accept these electrons from a base.

eg.

H

\\ - ~ : ~t> \-\+" \

\-\

BASE

ACID

Ostwald's, Dilut'ion Law

Consider a solution containing 1 mole of a simple binary weak ~lectrolyte

.

AB in volume V of sOlution. The temperature is kept constant~ Applying

the law of mass action(taking the active mass of each ion to be its ionic

concentration) we have:-

Q

eX

-

V

.'

. .,

\f-

v

-4

\'35 x \0

\0

~ -3.-3

\ • '3 5 x \ 0 M 0\ - !.,_ .

.u

==- - -

[ ~ . . \' \' \_ ~ '\7\I"\O\~ o..~ ·~t

to ~:- J\ ~ ~ ~ ~.~ t"~ 0-.\ ~·~o C \. (_'L~\ 0·"" ~ '.3" W (A..~'<..~ d ,~

'.S Y\Q_c~5 ~\. \,\.Q..., c"o ~~o..:t~b. tc ~\.... ~ a.V\I\.c ..... ~~ + \"tiN'- ~~ e_ ClC ~t

\A)~~v'\ cI... \~ S''\A.o..\\ .~Q..., ca.'" l\.~~~.,,-.\.V\.l..~Q.., ~~ CA.\\\~ c.\.-~\ \J.\f\~\-~'

j: (\ C~ Q.... o..~O\.t'Q..; 0(::.. \. 3 6 X. \(J-'l. ~ (t -..,() :::.- \

LV0\."- ~~\s a..~'\'Ci\N\.~'t-\O~'\ Os.tw~~\S ~-\~u..\-\c.'\ lll.w b.",~s

o('l.... . ~

- =!:::. \< so e/... ~ ~ \<.\1 uV'oJ.. .0( -== \ Kv

\I

---(~~S i.t.)""~{\ V:: \ 0{ ~ lK ~. 0( o'£- c, L.uQA.\-(

'" }

. ~\~\:-\"O~~~ \11\ I/V\.c\o..t .sc\u.\-.~o~'\ ~ fK .

K -to\ 0... wQ..o..\( Q...,\IU:..-ic-t'o ~~ \~'N\.C\.'" AS v,N\C·\,a.",~el '~ct O~'\\':)

M (~.:\\u..'t-i. 00/\ \,,,,,\: ~ so o o Cl.Uo, I:- \ M 0 f c I:-\"~'t' . ~\ I1z. \-~ \'\ \u- 1-0

\:'\... e, SO\w\-- ~ 0-,\ I ~\,) ~;;\ W~~.A\ ~~t..-

~O \~ Q..-<t/;\ \. ~ \:, \- ~ Q •

f 0 t ~O\~\oct.. s \ c. c.Lc:.&,S

~' H'4S I wQ.. ~u.\,)Q., , \-\k .Ie t\S-

. -

[\-{k j [\-\ s- j [\-\~s 1

L\-rt 1 [s=-) _ [~s-j

-\~

lO

, .

M~\ \-"\ ~\~"\ ¥'-~ t~ :t

'2.

[\-\k:\ [_s-=j

t \-\.,_(~

~his is Ostwald's dilution law in symbols (1888). K is known as the dissociation constant of the weak electrolyte at that temperature. It is found that for weak electrolytes, ~ ±s fairly constant, but for strong electrolytes there is a wide variation in its value with changing concentration. In fact a weak electrolyte is often defined as one which obeys Ostwald's law, and it was the inapplicability of the law to strong electrolytes which first raised doubts on the Arrhenius theory. K has no mean~ ing for strong electrolytes, .which explains .why .wh eri we , meet _K....italway.s has a low value, usually less than 10-2 mol. dm:3 Since K varies with temperature the latter should always be stated unless it is 25°C, the arbitrary standard.

The Strength of Acids and Bases

K is an important index of the strength of an acid of base and is preferred to the degree of dissociation because K does not vary with concen~ trati:,on. Thus the relative strengths of weak electrolytes(acids and bases) can best be determined by comparing their dissociation constants at the same temperature.

The degree of dissociation can be-calculated-at -any conc~ntration-fTomK as below.

ego Calculate the degree of dissociation and concentration of H+ in a decimolar solution of CH3COOH at 25°C, given K at 25°C is 1.85 x 10-5 -3

mol. dm.

C \-\3 COO H

-+

"'

~t'o__ () S\--~Cl-\.~ s c\J~\-~oV\ lll.\O <:J..._"L

(\~\\J

-

-

-

-

0(4 t· 25 x\O.> (\-~)V
V \.0 ~,,'<- \JJ..u.M.e., C-", .\'; \ Cc<-.\ a.~ "" ~~ ~ ~~Q._ Q\ o.~~ - \0 \\~~.
• d..._'L - \. &5 x\o-s Cl-J) \0
• • b.. -~
• ot..~ ~ \. S 5 ')(. \0- oL.. - \ I 85 X \ 0 :.0
• 4
-~ o · 0\ 35"
0 ...J.....::. t <;5 X \0 =- ~ .li

CD~S\d.~\" <tv\' <.\.tv..~~S $C\u...\-\Oi\ e~ C\.. ~~\.\< ~3.. H A .

\-\~ ~ \-\1..0 ~ - \-\~O-+ * {1-

.'. \<.~ - [~30'1r~ [A-~

[ \-\ fl1

u~~.Jc_'\"~ \-0 ~ ~~c.tll\.~ ~~~ -~ ~ ~ ~\'*

[H~O~~ ~ '['t\.Ic~.,

I

_ [\-t'cj L~a.S~

[t\-~"\

[\-\1...0"} ~\;) lL~~, c...o..\\.\",~

KCl

~~ rn.:I.\o.~ \'"" o..~'- '4,\A.wu..~ s·c\u.\-~o~\ {~ 1..0Q...o._~ '\)e..~) ~) \::~

'oC\.5:~c-~v... ~\:-.~ ) ~~ J' ~ ~"" ~ ~ 11..,0 ~ n\-\~ L AU- -., I

'J '(f t\ .... ~ \:) -.; U \\ \I) ~\ \N"v\ ~~: .,...

\<. '-0 ~ I. ~ t\ -t-j [0 l-rj [\)"1

, .

-:= [fT~1 [0 t\-1 C.~o..s:~1

\5> ~ -...:.""""- Q..D

KG\- ~\_ l ~

\... 0 \ c \ -::.. \ k- ... 0 0

\. ~'" cA...... ~ "c;L .J.::' \ ,<,-'0

\~ G,~ ~ ~~ \J~ I I;\.,,_ """'~ <>-~k -j: ';.n, ~ ~ w<r \:4- ~ \0..'-0 \J ~) \:\-.Q...- ""-0 ~ \:,o._, ~ c. - ~ y, ·

1

The Dissociation ofifJater.

If water is purified of ions - by an exchange resin - its molar conductance falls to a steady, very low value. That "this slight conductance always ~emains ~ndicates water always contains some ions, believed to be for~~d a3g-

H 0 H 0 - _ _:.,,_ H 0 + OH- . H 0 '-. H+ OH-

2 + 2 ,,~:._---"" 3 +. J.. e • 2 F--"' +

Applying the l~~ of mass action at constant temp. and taking the c~nc. of ions (mole dm. ) as their active massesg-

, . .

Therefore

r: +1 t· -~1'

\H 'iOB =

' .•. );J _

Now CB 2Cl is effectively constant.

L~ +'r r _ ....

Therefere H':' tOR ,\ = K \ constant =

lew = ionic product of water.

Kw (at cons~ant tem~.)

"Each ~olecule of water gives one H+ and one OH-. Thus the concentra~ tionof these two iQns must be the same in pure water. Their conca is

-'I -J 0

about 10 mOl.d~7 a!725 C. 2 -6 -14 2 -6

Thus Kw = (10 ,\, 10 ) mo 1. dm , = 10 mo 1. dm ,

A solution containing (H+1 great~r than 10-7 mol. dm , -3 is acidic, A solution conta~!;-ing :,:!:t !_~ess than 1 O-~ mol. d~. "-3_ i.:s +~lkaiil}e. __ -" At neutrali ty elf .. 1- and LOR _j are equal. rrow ev e r' much LH J and LOH ,I

are altered by the addition of acid or alkali, Kw remains .constant at constant temp. but it varies with temperature.

~drogen Ion ~oncentration and pH

I~d~_$~:rt?ing th~ aci9:i~r..:,or alkalinity of a soJ,:u~,;!;q_r it i~1.&ufficient to g a v e I_R , . .! only s a.n c e 1._OIi , .. 1 can be _de~uced from I._OH,J = ,_10.(at 2SoC)

I . .p t h 1 . t' . i q+: ., . . '. t I H+ I 't

'n v a ew 0.... He arge varla a o n a n ~>. _! 1 -r; 15 c orrv e nn ert :_ _ 0

express it on a log. scale. The one suggested by Sorensen in 1909 is

now in general use.

The negative logarithm to the base is called the pfl. of a s o Ln ,

ie.' pH = -log ,-H-r-j

. . 10 1.-0. -4

10

of the

, ( -3)

lon conca mol.dm.

~ The c o n c , of.' f~+ Lo n s in t.wo s o Ln s , are (a) 1 X 10-3 mol.dm.-3 and.

() -10 . -3

b 5 ';:' 10 mol. dill. • h'hat is the pH of each soln?

(a)

pH 2

= J (b)pH = 9.3

A so lnt ha s a pH, o f' ~ '. 1 0_ gha t i ~ i! 3

a n s , H. ion o o n c , = o:K10 mo Lv dm ••

ion

conci

ego

Hyd.r-o g eri ion cone. of a s o Ln , may be found in various wa.y s , l"or a "Teak electrolyte it can be calculated from~as determined from the conductivity ratio or the vanlt hoff factor. It cart also be deduced by a comparative colorimetric method. pH can be found by measuring the potential difference developed when a glass electrode and a standard electrode are in cont~ct with the soln.(principl~ of pH m~ter).

The Hydrolysis of Saits.

Consider a salt }!lA' disso cia ting complet ely in a.q u e o us. s o Ln , -. as f'o.Ll.o w s 9-

il.Jl '\ w c .. }- -

hA -----~'-lVl + A

also

These 4 types of ions present give rise to 2 further equilibriag~

The posi tion of equilibrium in the above depend's -on the s-trengths pf' HOff and I-IA; 'If MA i~ th'e salt of a strong acid!w-ea:k bas ~(NH4 01) t.h an an acid soln. results as EA is fully diss~~iated but~OH is o~l~ p_artially. dd s s o c i.at e d ; _

:f-iyd~olysis can be regarded' as the opposite p r-o c e ss to neutralisati,on g-

. neutrali~ation

Acid"t Base ---:----------:~ Sal t + l,vater

...-------------

hydrolysis

The Common Iou·Effect

Ifastro:q:g electr~iyte'isadd~d to asoln. of a weak electrolytes-so chosenS-J_-ch'that-on-e of'-:,the ions Lri t o which it dissociates is the same as one from the strong electrolyte,.thedeg~eeof di~~ociation of the, weak electrolyte i5 decreased as a result of the common ion effect.

~ ego Consider a s~ 't , s o Ln , of H2S. Ignoring thet~~ostagedisso-ciation we can express the dissociation'asg-

H2 s,i,' - 2H+ -} S

·thus KH ~

--,.., ,;:> t:..

=

,-- - -'"'1-

js-

~-- --'

(const.

temp. ) .

rU2S1 L-. J

combine s o: that.

f u+

c o n c , 0 u-

r -, ':;. r --,

, T+! . - i ~ h J' ,3 -;

1..,....... • ;_ .: _'

Ls .

If a strong acid,HCl,' is now added greatl~ increased, thus~-

E-Cl---_} u" + 'vr<l Th u_+ - S

_ • -_. 1 us kana

to the soln. the

---~-----.-

,

again

equals KH S so the conca of> S
2 "
relatively large and shows only
-_.is approximately constant. Thus ioilsde:oTeas e.

The

value -of FH 81 .Ls

, - 2 _I _~

. r+i"-( :-,

the product 1¥,) ;~S J

little

r :7 LS \

: -"!'F'

'fo change,thus 1

is appro x .;;:< -=--=-:-2--

. i p+!

• _.a. _.i

and

a 10 fold

increase in

;- - .... r

reduces LS to 1/100-0f' its or:iginalvalue.

The common ion effect is not limited to cases where the dissociation of the weak electrolyte is decreased. ego if NH40H soln. is added to a saturated soln. of H2S, removal of H+ ions by combining with OR ions from the l-ifI-Ilj.0B causes the H2S to dissociate more. Th i s is ma d e use of

in sYBtematlc qualitative analysis to separ&te the metals into various groups.

NB g - 14hen HCl gas is bubbled into a nearly sat, s o Ln , o f' Na C'L, salt precipitates out.Is it the common ion effect? HBr gas will do the same as the HCl gas-thus not wh o Ll.y the common ion e:ffect.iJhen these very soluble gases dissolve and dissociate9a substantial no. of water molecules are used for hydrating the resulting ions9 thus the effective conc. of the NaCI is i:._creaseci and so salt ·is precipitated.

Consider an aqueous s o Ln , of a weak acid :rlA r e x , Lurray pg. 41

\H2~JiS_co=sidered

r}I -0+ rlas i H+ ! ~T

L 3J, ,-- _! rca

;

constant because

[H+] ~aseJ_

it

is

in

large

excess.

yutting

=

B

aqueous s o Ln s ,

BH+ -+' OH---'

of a weak base TI, we

LPH+] 19H-]

Kb =

have~-

[~ciciJ rOll";!

@as~!

=

Similarly, for

r ,

Ka x Kb

=

-14 2 -6 0 ".

- 10 ,mol. dm. at 25 C--the ionic pr6duc~bf

usually represented in their logarithmic :forms,

water. Ka'and Kb are

pKa = -loglOKa; pKb = -10~10Kb,

hence pKa + pKb = 14 the lower the pKa value, the more acidic.

If a piece of metal is placed in a soln. of its ions, a potel'lt-ial'dlf'ference is. set up between the metal and its solution. ~his potential difference is called the Electrode rotential of the metal.

ELECTRODE ;POTENTIALS

of

Z 2+ n

ions

Cu2+

ions

The negatively charged Zn rod charged zinc ions round'ittb

attracts an atmosphere of pOBitively forman electrical double layer.

rr ( ) -- ,\. Z 2 -{- ( )

LIT\S ,---- n a q ,

+ 2e

The three principal factors affecting the position of equilibrium above areg ....

, , '

1) The nature of the electrod~9

2) The concentration of the metal ions in the solution, )') The t emp e r-a t ur-e of the system.

The electrode potential of a metal/metal ion system cannot be measured directly because another electrode is needed to complete the circui t and \'Iill have an electrode potential OI~ its own. The standard electrode potential of hydrogen is taken as standard and is given the value of zero. Thus the standard electrode potential of any other element is then expressed in terms of the potential difference(in VOlts) existing between its electrode and 8. stand2.rd hydrogen electrode.

4

. ~ .

Standard electrode potentials are wh e n the element is in contact wi th a molar soln. of its ions at 2SoC.

'l'!hen elements are arranged in order of' their standard electrode potentials 9 the resul ting list is l:::I1own as the electrocl:emical series. _ The equilibrium existing between an element and its ions9 ego reduction

H2+ + 2-;- ,. lifi

o~idation

is a redox

system.

The electrochemical series is part or,a much larger reduction-oxidation series called the Redox Series obtained by tabulating standard redox potentials.

increasing power of reduced form as

Oxidi's ed form

T- • + - -;;::=======-

"",1 + e "

K+ + ~ -------,~

Zn2+

Reduced

form

Ee'jV -3.04

-2.92

-0.76

-0.14

0.00 +0.15 +0. 3L~ +0.54 +0.77 +1 .07 +1 .23 +1033 +1~J6

Li K

a reducing .agent

+ 2 e :;;~;======= + 2e~,

Zn
'" 8n
H _.
- 2
~ 8n2+
" Cu
"' ;..
21 increasing lpower of oxiidised form as ian oxidi~ing jagent

! 1

\1'

Sn2+ 2H+ LH Sn

cu2+

+ 2e
+ 2e
2e -
+
2e- "

+ e
2e- "
+
4e~ \
+ + 1 .52

+2.8'7

In theory any reagent on the right will reduce anY20ne on the left provided the latter is b e Lo w it in the series. Thus Fe + ions reduce bromine to-Br~9 but not iodine to 1-.

ConverselY9 any reagent on thE' left will. theoretically oxidise anyone on the right provided the latter is above it in t h o series. Thus an acidified-~olti. of ~otassium permanganate9 hut not dichromate9 will oxidise Cl ions to chlorine.

Two points to note

1) The series is of standard redox potentials so i:f c.o n.c ert t.r-a.t.Lo n s and temperatures differ9 the order of tha syst~~s may differ.

2) The above gives:rno iEdication of rate.

Standard Electric Cell Po t ari t i.a Ls , The Eo L. F. of Electrochemical Cells. The Daniell cell consists o f a Zn plate(cathode) in a solution of'

zinc sulphate and a Cu plate(anode) in a solution of copper(ll) sulphate, the two solutions being separated by a porous partition.

zinc

plate

/ .

.. -~\---- !

,

i

.t..;

--direction of flow of current

I

-!

I 1 I' --

-- .. '1-' ---

1--' -r-:

:---)1 .------~~j----I !---I

I 1/ ! ! '

i I V: I' i

I 'I~) I' I ( 1 1 \

I '} I _---copper -'-:!;J_

! I/, --+----

~. J'-!'-\'-~__ _ __ J

. ~ 1 - .J._ 1\

z~nc su phalJ8

solution \

porous partition

copper pla.t~

sUIJ2hate soln.

The current{not electrons) flows fTom the copper plate to the zinc plate in the external circuit. The process is accompanied by an increase in concentration of the zinc sulphate soln, due to the dissolving o f t.h o zinc plate and the diffusing of sulphate(VI) ions from the copper(ll) sulphate(Vl) soln., the latter becoming less concentrated9 with copper being deposited on the copper plate.

The e.m.f'< of' the above cell is 1.10V. denoted by E. The standard e. m , f. of the cell is c o nv en t Lo na Ll.y obtained bysubtr<;-cting the standard electrode potential of the negative electrode~one on the left hand side ie. oxidised state) from th~ standard electrode potential

of the positive electrode lone on the right hand side ie. reduced

s t.a t e },

For the Daniell

Zn ( s ) ! Zn 2 -l- ( aq )

cathode

Cell~-

2+ I

Cu ( a q ) I Cu ( s )

anode

Thus

E =

-s ..

E ~

reduced

state

"N'G .1Joxidised

state

E. =

-<:}--

11" ~anode

",B-.ucathode

E = E:Z-:
rns
= (+0,34)
= -!-1 • 10V -;f--&--' Llhs

(-0.76) V

The sign of E is always the same as that of the rhs electrod-e in the cell diagramo

------- ......

1

2:?~ion tot4e'eq.uilibr:LUm that exists between a sparingly

5CJlub~l:0 saJ_·cin." ·the·~olid state and· i tS:Lons in solution •

. _. _. . Cvns':CJ.e:r <:i. s~t~~at~~~~o~utionOf a·binci.ry electrolyte lilA in contact

",d th a~-'~'~ce3s' :of undis.soh}e.d-soiid.at.. constant temperature:'r1A(solid)~~M~: + 'A-

the

coneso

<:

of Lrid L vidual

ions as t~cir activ8 ma~se~=~

But the a.c tzi.v e r::fsL; (Tl~ arry solid is constant at constant' temp ..

'I'h e r-e f'o r c , U'\~l~~] "~. c on s tia.rrtr :: S.P"1-1A,the SOLUBILITY PRODUCT of t h e s~l+:' r.H <ot-- tho..t- ';'en''''

"eg.·s:·p,~:,:"" ..... ~+j ~,i,j. - 4 ·~10.:.13 mOI~ dm.~6

. t' ~-9t- "*,,,.

U :;..,:.,..

-. -"

~U-;.e_\.r~~')<>:C.j._;;:_-UH::e ~·t ScP", is that it indicates the maximum value of

" ;. ~

io.r::i.~; :;_)Tc.o.ncti: in a s o Lu t i.on.s.Kn an un s.a tu r-a ted solution, theio:l1ic pro-

..

duct ,.,iJ.l :'1.:::..ve a_],OY·3:;_~ valueoS.P. can be applied to sparingly ~oluble

. .. ;

elec~rolyte30nly b8ca~s~' in thes~ cases only are ionic co~c~~~uffi6-

i·:;::}·i-:,/'7 lo~-'i t.o be te,ken as t h eLr- active masses/Thus S.PS,are always very

s.p.

v~ries with temp., .the latter always

bd_:":~ q uo c e d i:f o t h e r- t h ari 25° C •

. 1'"

8D.lcvlation 0:::- S.P.

~ Q:.~'R>_"''''''~~'''-.-&'"1o.~-:=,"---=--_Q"~ .• _-=---~ __

soln.

6 -3 . -3

contains. 1 •. X 10 . g.dm.

S0lubilityo~ AgCl -

, '~.~, ,~'5 d-3

., In I~IO mol. mo

. ···10· 2 -6

,.;:102>(10 mo L, dm , at 20 C.

A DE 1 i cat i ~'f JL~~,._.i2_..£'!:!~~)~ ~ 1:_,'1 t i v e Ana 1 ys i 13 .

Q.E9'.i1.?_:~_ S, P 0 of s:'1.ve:;,~ chlori de 9 me r-c u r-y I 1 ) chloride, and Le a d chloride

. 0 ._ 1 0 2 -6 .. -18 . 2 -6' . -4 . J' -9

at 15 C a re '! 02)<10 . ?,0IQdnl0, 2",5)(10 mol. =. ,2 .. 010 mol. drn ,

r-e s p e c t.Lv e Ly-. Th-:.-'.s i:' any of 'che'se 3 m e t aLs a r-e vp r-e s en tvd n the solution "hen RCb. i:3 >.I'::lc.eci9 they ,,;ill be p re c Lp L ta ted as their chlorides becaus e their S.P~owill be exceededo S.P. cif lead chlorid~ increase~ with temp. explai!l::'.ng '~!hy gp~.1 50J_n. mus t be cooledbe:t:o.reproceeding to gpo 11.

GJ~0t.1.D. 1~;

, __ =~ . ..o;" .. ..,.....-.:;:,.-.,..,. -

3Up~prG;:.GeG

';:;ho p r e c f.pd t.a t Ln.g agent"is'H2S in the presenceofHCI. HC!

2- .- .' -15·· -3(. '.

the S ion c o n c, from about 10 mol. '. dm , a ts value in a

----

~-: ..

• ' SOLUBiLITY' PRO'mJCT "~;--:'l~::_"'~~~~"-

, ' ' " '':'''25 ' -:0.

s a t ur-at e'dcs o Ln .. "a t v r-o om temp.) to about 10 mol. dm.'Si.n-C-e .. t.h e-vco nc ,

e f' m e tia LvLo n s vd ri 'gp~11 ::solns.wiii be about 10-lmol. drn , -3, onl~'

.t h et Lea s t ' solublesulphideswiih'S.P.below le-26 ~ill be pptd. The others willrernaih{nsoln~Thu~ s~iphicies of Bi(10-72),Hg(ll )(10-'54), Cu(10-45Lcd(10~~9),Pb(10-29),Sn(10-:-28) a pp e a.r- in this gp~ whereas thOS'8 ;a::f,Ni(10-~4hzn(10 ... 23,) ,Co(10'-:-22) a~d Mn(10o::-15) do not. This

eriables us to li~itgp. 11 to 70r8 metals.

If the conca of Hel is too high, then dissociation ofH2S may be suppressed to such an extent that even Pb9Cd,Sn, sulphides may not be pptd. in this gp, Thus,after treatment with H2S,the gpo soln. should be d±i.1l.uted and-teste~ again before going to'gp. 111.

Group 111

He~'e't~_'~-pre~ipitating agent is !'JH40H in the presence of a high conca ~f NH4Ci.Thelattersuppresses the conca of OH- ions. thus the S.P. of more soluble'hydroxides are not exceeded and their ppts. do

not occur. SoP. of'CriAJ,._~:B":e(111) hydroxides art 10w(10-30, 10-3J,'0""3~ i~'j ,

respectively.These 3 are'completely pptd. as their hydroxides.

Group IV

, -i~,

TheJ>.recipitating ici'gent here is-either H2Sin the presence of NH~~JBi i

so Ln , or is ~mmonium'~.sulphide s o Ln , In either case, the c o n c , of S ion /'

~_high and tho~e metals with insoluble sulphides

'; ·1: .', '. ~ -"; .;. . '. .., 'to: • . . .

pptnn ingp.II (:rJi ~ Co, Zn,Mn) will be p p td, here.

··.:.:.f ;.

which esca'p~d

, ;"

f / ;

The precipi ta ting ag cn t here is ammo n.i.um carbonate, )rhich gi ve~ a

high c o n c , of C( ~- ion in s o Ln , and brings about tft' cfmPlete pp tm , of t h e car.bonates of Ca,Sr9Ba~which have solubility products of 10-8 J-1-o'~~~

8< Xl 0 .... 9 respe~t~ vely. ",'_r/ ...:._~_'

_//

.~--....___---..... ./

Solu,bility of Salts of Weak Acids in Strong Acids

>

It is an experimental, fact that sal t0f weak.a:~idS are much mor'e sol-

uble in a s o Ln , of a ,-S.trollg .. .a c.i d ~_tn.a:n in we: t-e r , Calcium phospb.a tie is only ~~;_;;'i:ngl·y--S-i)..b:b.r:e .i.n wa t e r- a~ roolli_.t,eb-p. 9yet dissolves,~reelY in dil. HCl.This can be explained by consinering the equilibria existing in the .s o Ln , Vihen'solid' cal_c_:j_lli-n"Phosp4it'~e 'is added to water,w'e have;-

. " ,.,:' ",'~ '2~+ .. '''3' , /'

""Caj'(P04)Z:SOli,d ~3Ca. ' +' 2P04- ',/:

,'~a[ca-243fo4-Jj2 ':_ 3.7.C ,"('P"O )' ="10-20

" ,aJ' ,42._

Group v

_I

also

H20 tF*"/ ~ oa/"

I

i

t

I

}" I:

~f ~i+ and PO~- t:a.kes

/

Under thes e ciryUms'talliies ~~-v-e-ry little combination place" because )~~lJ.~ exp,re-ssion(ttTJ,:'i (PO:~) soon

" , . ' t~3?O~~ ,

corre,spondipa /to-IC. ' . ..l

" ' ~'"t>'" -I;I 'PO '. ILP04 ~ -:0.. 3H+

, , '; /j 4 j +

/ ,'", /

, /

/

,//

the value

83

-

~,~ T, ~,rh t;>. +----GI---·;· raising--t.he-c:onc..-o~~-:--

.:~O:!J,G. -Co 3. relatively high level. This ca'_;s es H+' io~s and po~- ions to r lli!,:Lt;e ill large no~~ to 1~0_r_31 undisso·ciated: molecules of ~P04' so that

th~ e;:p~~essj_on[l'\+J3 [?Oi; J is"restoredto its original low value 6f

'. ',_.'_

[H3 PO!:,.]

:{(;:'T PO In the process t h e rc o n c , of PoJ4-', 1,' o n s . is reduced to such a l,ow

-'--J L!. C

7aluet;ha tthe 'ionic productof'~ CaJ (PO 4) 2 falls well belo,.". i~s SoP.

causing more of the solid c a Lc Lum iph o s pha t;e to dissolve. The interaction ~H.:\·i::-:£"":;:!} trh o vari.ous_. equilibria c o.n't Lrru e s UJ."ltil a high c o n o , of ortho-

..... -.._,__

p'ho e prro r-Lc acid molecules exists in s o Ln , and much of the solid .,c~J...c..:Lum..~·-·

_--_. ,.

phos phace. hasgon9 into ''sb-.l.n..,..__

-'~

Thus the overall effect oil the>HC.l is to suppress the already small.

dissociaition of the w e alc o'rtb.o·pho~phoric·~~ia-'-by,,_means of the c ornmo'n

ion effect: and t.h e r-e by t·o 1 o ,.".e!,. the 'conco of po~--·~·ons-in.,the s o Ln ,

eo that more of the salt dissolves. A similar explanat~on applies to

the. solubiJ.ity of s a Lts of other weak a c i.d s j e g , oxalates and tartrates.

!~ INDICATORS

An. Lnd.l ca t o r- for aCid/alk:.li ti trations is a substance showing different

colours

the

·1, " ' ' ' ,

pH":liOf its environment alters. It is usually·aw€a.k".

or_ga,..."'lic, a c i.d

»> -_----_.---

di s s,)'cia t e s

or b a s e and can be regarded simply as a substance which

thus ~._

HA

--,

.J.

H' + A-

colour 2

' ..

c..olour 1

Crre, -::;;eli er 9

.i ri ,LL

s~rongly aciqic solns.9 c016ur 1 pred~minates,and

In 10w concs. of H~ colu~r 2 predo~inates~ Indicators are weak electro& Ly t e '39 -varying g .. r e at Ly in 'cheir dis s o c La tion ,c.oI1:stants, which. means

+hat they c ha nge colour over' widely different bands of pfi, •

.. ~'-'- ..

-~.. ""T"---~I--'-"'I-__"'-·--:---."...--~---'~---r----r--"""T-- ....... ~-..,-~.....,..,---------

ii ? /~ Ll- 5, r:. 1""" .. 8 G to il 12. .3 'It-

;:)1\ '""

\. "

.J,.

H' ion conCa of the centre-pte of each range is calculated from the

-:,~alue of the

dissociation constant,

since

A-&··t~e:rn'-:i:~C'Y]~S-().;t.--C..o.J..ot~:K1.....p..l:U::~c..1.e:. "iiI:.i.l..L_hE'lj~~e1T~--"'_~ in equal coric s x j Le ; C~1=(}.=jjCH+1::: ~-_ ..

distilled water is~

K .'

indo This explains

alkaline to methyl orange(K. d = 2

. 1n n .

. 'r ~ ".

why air-free

-4 -3)

10 mol .. dm.

pH 3.7

ie -e,

n eu t r-a.L to litmus{K. 'ct = 10-7mol.dm;3) phl 7

1n 0

i:tcid t? phenol phthalein(K. d = 2 10~10mol.dm-:J) pH 9.7

. . . 1n 9

T:Lt:ratioli Curv·es

1 }Strong Aci.df2_1:I2£ng.J~li

':t

If' we start with 50cm-;;' of O~lM HCI and run in O",lM NaOK, the results azre

as b e Lowj -.

y'<?,.bume 0" j¥Ul!~li added( c~

.. _- _/' ...

.' -

.-,/._ ... A·

_._ .. _..,..- -' -~-. _.-.2-~ __ ..

-

~ -_·: .. -.-.49

_..... .~49-,>/r ..

- ... --- .....

. _.-". 49 o 9 5~-·

50,,05.

5100 55,0

+ . -3 Ell
H c orrc , mol.dm •
. '-1 l
10
3 .. 3 10-2 1.5
5 10-3 2 .. 3
10-3 3 .. 0
10-4 4.0
10-5 --'-
S 4.3
I .. . '-7
rr
I 10 I
2 10-10 9.7
10-10 10
~-1 1 1 1
10
2 ' -12, 11 .7
10 ;2 UleaJ<" Aci.dLS~r( ,ag Alk_§l.]. L

eg" acetic a c Ld titrated with s o d.Lum hydro.xide so In .• ;._2Strong ACid/yfeak Alkali,

ego Hydrochloric acid titrated with ammonium hydrOxide soln.

T±' tra tj~u:::Y...aa. can be constructed for the ti t r-a.tif.ori of acid with alkali and are as sfrown b e Low ,

r \\ I

14 j n

/

.-.---.-~----------:

ss

-

-~____ 1

--~- _j

::.hl~ak ~c~~h:ak. ~}-kali

eg,~ a.c-e.ti.i c acid .. ti t r-a tre d with. ammonium' hydroxide .s o.Ln eo

I:u titrati:su.;: 'ide require -the equiv-alenoe p e i n tr c Le , whait volumes of

the two 'S c) Lu td.o rrs a re chemL:.ally equivalent 0 So i.deally-, we require the:. 2,~~~:of th ip.dic:8_·:~nrCi:e9':when ~ t crhang~Ei._. c o Lo uz-] ,to c oLn c Ld e with the ·equiv.alence point<-To- aehieve tpis,we need an Lndd ca t'or- that showsa sharp c o Lo u r: change at the right pH"

·t) StrOl~_Acid/ Strong Llkali

\<Ie need an i;).dieatoJ' which (,hanges oolour between pH 4 and pJii 10. Thus methyl .:->r8.nge or phenol phthalein would be sui table.

2 )Weak Ac:Ldl_~tE2.r.~~~~j.

Indicat,or-,---- Phenol phthalein pH 9

Indica tor·~-·~~ MethY'l orange lJ.R 4 o.r-. 5

'--

.i2 w e~;~pidL1f~~L~ka~i

No. sa tis:fac.t0l:·-:· L'1.dica tor--~void this type o'f"-ti t:raljou.

Po 1 ~s is;:_.A~d:d:3

Consider the titration curve ®bt~ined when. orth~l'hDsphoric aeid(HJP04) Ls '(j~l +r-a t.ed wi th. e cc.Lum hydroxide soin:..This curve shows two rapid svli.ng5 in }III, c o r-r-e s porrdd rrg to the first- and s e ee-rrd stages o.f' the acid ~ s dis s o ci a t5 ou_,A thi.rd inflection of the cu ev.e , t.h Ls time ve.r-y indist:i.n.·~t:t 00C1':7.'.'::; in'8 t-li'()Tlgly a Lka.Li.n,e s~L"1.'Fb.i~ .qu,r,¥e @<~plai~ why methY,l o,:r~~ ~:::i:;JJ]_dBtE:C'e~ the 'i'i:rst hydrogen havip_.g b e en, Feplag.ed, phenol pbtha+e:i.n -::'he s e-c-orrd h-:rdrogeE.rep.laceci~ arid nQ,indiQat-or is suitable {or de·t{HI~tr-

w.tl.erlt:;odiu:.'11·~car;bonate is"titrated with a o,tf;rong a.e Ld j a curve with twa reflectic.ns is o b t a Ln e d s Th e carbonate changes to the bd c a r-b e n a tr.e, e:'e . c.1.1)ou-t~··PB: 9 ~ sa phenol phthalein \'Vill respond; methyl orange will detectt the second stage ~f neutralisation at abeut pK 5D

.,A'" t-.... \--'.\,.." r· ".\ ::." C' \,-\~' n \ ,\ \.)1..\ s '\: t: _ ~.~f. '';{\, _

_ \_\_~ , '..l, • ~~" >J Q... -s .::J ..... ""~ - :"

f

: r--

. . .---

-Th.e S-e- a.r-e- --s o.L u t.Lon.s whi ell res i s t charrge_,s__._in ·~.i.ru.:L.._crr--on--'t~

a.d d.i t.Lo n o f' a c t.dtor- a-Ika:l'i.,They usually consist of a s o Ln , e f' a weak

a6-i(d or' a vieak base in' tlli.'B p'r-es'errc e of on e of its salts, eg. sodium

·a.c·b'tat:eaud a,:.:etip··ac:l.d.Jj\-ij_:'<tu.~-es of t,"~ ac Ld salts are aiso used.

To see hcnv a b u , .. :fer· s oLn , . works, c orrs Lde r- a weak acid Ff...A and its sal it:

Buffer Solutions

UA _. --~. H+ + A-

~~~-

~1A ---7' :t-.l+ -;. A-

[Ht\] re 1

/ o r::-. • . W' 0 (I \r,: r « r ~}I. \-,,.. ~ Q.. A.

C.O /'I c.. . " -r ~ "... \A'_' [J. .......

.~:r,_.

.. ~.

o ~- So.\\v

, r-' .

I

n o t much ·affect.eden cliluticn., s Ln c.e the.. r-e La ti v.e

can,c - of". a c sd and .s a.L't r-ema i n c on s t an tr,

.' c, If -a.ri a.cti.d is added co a buffer soln.?most of the . added H+ ions will combine .. Ji-:h A- Lo n.s to give. undissu-ciated HA.~:ii.EL_(1)rd9'Jr'::i:tD._keep

r 1~ '·+1" l..-ft· .... 1

-~, _- -~-

.' i:::~'l ',' at: j_-!;s: constant. value ~p' arid the pH will be little: alt:·e:r-

[ \1. H _. . un

ad 'a's a r·esu.lt,o

If' alkali is added to a buffer 30ln., most of the OH- ions are rem~;-ved fr-crn the s o Ln , by combination wi tb. H+ to form undissociated

-I-

molecules of' wa t e r , further H- being furnished by the dissoci.ation of

ID'l~ so agaiJili trl1e pH. cb.arrg s s only slight.ly.~ Thus the s tcab i.Lf tv of the pH. c arr be a t trr-Lbu te d tro the high c o n c 0 of A-ions, whic.h act as a trap

-~

for added H_..'. ::i.ons.". and the.la::-ge cone. of' HA molecules, which provide

. ....

a Tes ervo·ir·o.I J:i '. ions for c omb i.nd.ng wi th added OH- ions.

The chief use in the ~La-bo is f o r: making s o Ln.s , of known and c o.n s t.-e arrt pH:~By the choice of e u i.tza.b Le substances,we can make buffer s o Ln s , of any pH b o t w e an -l. and -13.These buffer solns. can be used to calibrate indicators o~ determine the pH of a soin. colorimetrically.

It.. is important to be able to calcuiate the pH of any particular buffer s o Ln . and also the composi tion of the mixture needed to make a

buffer 501n. with a given pH~

. -fir:l'

- .; ~

'.-------. ~

::~- _.--t,.

11-" - ~ ,~.~ . t#-.~"""~ -

....... .

C':,-,.- .. ~ .

_ ,. __ ~-1..- __

Tl-.tUEl pH. clepenc!.s u po n the ratio c f' c o n c a ,

. 1 n T_-+ • K

eq uamo Laz- c orrc s ~? c ortc , '01 ri.. lons::: TTl' 0 1"...H..

of acid and salt,and when in Thus the value of the dissoc-

iatj:2n c'oflstant'is p-redominan.Lill_in£luencing the pH of a buffer s o Ln.,

,:,-

(""\"_ .

- - ... _ .. -.. .. :'".:':-:-."

("\ t, 5"_

<;'':;'" I.'J. wh a t; proportion"s r.1USt-- O~i:rvl solns,oi'acetic acid 'and sodj]~m.a..e,e'r.a'~,3 'i)e m.i.x e d in order to obtain a bufferHsoln~~H:r-J4T'-.">:JJ-':?'---~-------

(~; - - 1 8 .:~,.- ·-~5 . '"-I , __ '--3) _.. _--_..~_______, . ~ ..

\ -,~_ ~ - • '" . rO., ! 0 "'10 J.... ,~CUll." "-- - "

- .'.d.AG . _- .. - ' .. _- .

'. l Or~ .'

~ 10

- ~D~~o" K\\ Ac.:-~ ~ t-\ ::loC\lO t ~~ X lO> - 4 "3

~

-~ I, "J_C _I, "3

- ''""\:" I'..) '-\-

:::. 0" 4-5

, .

I "

I /". ..\ I i ,;,""\\}- j

......- "

'10 \. o ~\. ~ ,;" ~ t ("'" 'co\-,"- 0' 11>'\ \.

in medicin; and biochemistry,eg. blood

Ih.J-f'fe:r s oLn.s 0 ar e important

:;;~r.:;aiin.s--di.B..s.o.lVGd c ar-b o nd c acid and bicarbonates and also phosphates 'Which maintain it-s pH at about 7,,49 and a change of + 0.,5 would prob-

a.o Ly be fatal <,Thus injection:: into the blood stream are usually bu.f':f'ered..

r .... '_. ~ ~ ."_ . .". ~. I

.•. ~=~<."-'-=-

,

I

/

/

.-

El.ec.tI'ometri..:: 1'5_ tra tions.--,~~-..__ax:__e.._o_~..-

.-~ -,._--

_-- __ ~_1 )Can:ductometric Titration$:

... ~~~_ 1 -

---_ ~

Il~Dlv. measuring the conductivity of the solu. at various stages

of the titration aad plo~ting a graph as below:-

\ \)

ef\~ ~'<..

b

\\j t} \. <).\- a.\\<",,\ \ <). ~~ ~~ • , b) \N ~ I\. \( (.\c_~ ~\ \)..lrt (~\<. ~ s ((..

Has the advantage of being applicable t-o very dilute or c o.Louz.ad i s o.Lna.; for wh i c.h the usual colorimetric methods are unsuitable.

:2 \ P -'- r , • .j..' T' t t'

_) aven:l;~ome_0rlC 1 ra a orrs

This uses a pli met-er ieo a system involving a calomel reference elec./

t r-o d e and a special glass e l.e c t.r-o d'e which develops a potential direct-~y

_______..----p-Top-a:rtional to the pH of the soln. into which it is immersed. From readings of> potential differenc.e as measured wi th a po b en t Lome t.e r-ja tltrat±oll_ curve like those orr page 4 can be plotted. The end point is take~!1 as the point at which the pH- changes most rapidly with addee.

ti trs.:n-C c This method is accurate even when the s o Ln s , are d LLu t e ... and 8~n be applied to coloured or opaque solns. It has the further advantage of needing only small quantities of titrant, of being applicable ':/) many types of ti tra tion including .r e do x , and precipi ta tion reactions" a~d of being adaptable for automatic use.

...

.L

wnen;z.inc-metal is irr:rr:E':r.S0Q in ccpper{TI)su.lphe.te50lut~_cn~ ';:;.':8 net reaction invol:ves c o nv e r s Lor; of z Ln c l::;etal into rrydz-a ted z i.n c Lo n s , azrd hydrated copper ions into coppBr met.al~

i.e. Zn{s) + Cu++(aq)-4 Zn++(aq) + Cu(s) ~-----:------------(1)

\;(l:;.en thi.s reaction is dene ill a c a Lo r-Lme t e r , t1::;_e thermale:::cer..g··y evolved is 52.1 X.cal/mole of zi:.."lc.lf,ho',;ever,the f o Ll.o wd n.sr arra;:~{=;emeDt i.:: o e t

t- .'.L.' t' , - . a> ~ f - " \ • . - - ,., •. '::.", •

UP9 n e ~·~·laXJ.:l!lum p o t e n a a ; G.1i.IerenCe\.roD.j 1.5 101C: volts at ~:::> v~J...e.

t; 0. 7 _.. 1 / 1 ~ .

JU. ~.caL mo e OI Z1nc.

-'_';:.._

This arrangement is called an ~l-E_trodleF!ical. cell in which e Le c tr-o n s are transferred between t't-10 electrodes. The overall reaction in the above electrochemical cell is as in equation( 1) ar.d cari be d Lv i.d e d Ln t o

t~,'O reactions, each ~Jei:-:'b' called a half celi r9ac'ti0l!.!. .

::..:. .... :':lalf cell A In l:.alf cell B/~-

-!- 2e

++, \ ( \

r" i~._r:_I'· '?e eu ~)

v..... \ ~ - or-._ '-7 ' '"

~"'OT differ-eat c orccLna t d on s of half cells d i.ff ez-eri t .P.D. I S c an be obt:d.r,ecgthe greater the :t:.Ijo the sreater the t e ad en c y :for t he cell reaction to o c c ur-v By 'co;;',:;:-Jaring d i f'fe r-e n ti half cells with a i'i~ed h~lf cell, ::t.!1 o:.~der of' reacti vi ty of' ~'lalf" cell. reactions can be 'ob-::;ained. -Whe.."".. one ~.'l.alf cell is fi;::ed as t:.e standard l-:.~-·:.iro er. elGc~rode!plati(1.V;,m. f'J.a:ce iif\r::ersed in a solution of ~":.yd.rogen Lo n s t 11'':; .Yrith hyd.:rog'')!: gas ,:ubbled

t' r> ~ 1-. + _ t 1" "t 2'" °C\ ., --

over ne s ur-r 2..C e OI the 1:.8 c a.i. a a t mo s pn e r-e pres sure 2. :J j s -:::_:e 1:-'. :_'.

0-[ the e Le c t r-o c h emd. cal cell is de f'Ln e d as the sta.:-.,::ard e'::" e c tC'ode ~)otential of the second electrode-·-the P.I;. of t~:.e e t arrd a.r c :t~7(:rogen

-' t -d ....... , .r;-.1-~ r+·'-·~ '--1"'" l' --·-,t ' .. :t.._ ~t-:'r;- ~

G..'..GC ro ,e 1.5 l"aY.:en as zero •. L":'_"" '-'v~..:.<:or J...'.a. .;.. ce _ .":..t~.,. ,·e ~.l _. ,c:..c. .. _ .. c::.ra.

state(l atnos. press. for eases,lM conc~ for sol~tic2s:.

If the co~centrationc of the ions in the cell co~part=~nts di~fer from lmolar,i.e. are not ~n t~eir standard states,tLe F.=. of the cell will di:f'fer.Ee!ice' a correction !;;-l1st b e vme.d e to aCCOU:::1t for t1J.e <..~j_f:fering

ion c o n ce nt r-a tions. In ge:ceral? if t~"le electro c herri.c a.L cell. r-e e.c t Lo.n can be ,·rri tten a e g

1 ' )

-A, s

.x \

1'Y+() 1,X-l-{,

+ -13- an'~ -A \ aq...)

y t x.

1 I ) . ('

+ ~\s ---------------~- 2)

y'

the equation rel~ting P.D. o£ the cell to~ooncentration is:

\ r- -r: +-.i':c

C I ,,4!- r

F y '_J~,)

- _~l"0"""-

-._. J..L..I., 6e. -'/.

t-Y+J'\.i

\ "_D. '-

a t

,.,

25 - C, .::;.

is

0.059

. (J \

.---------------------\ I

rO .

C is the st~dard electrode ~ot8rrtial.

The above equation(3) can be USed to me a s uz-e ion c orrc e.rrtrz-a t-Lo n s Ln

solution. .

",;e have seen that :r'caction(1) can pz-o du'c e >sither 3.2. L<_;;:al/mole of

-_·..;-.,c 0"'" h e a t C-C,....-.y or .;~'=" c az-r-Le d O"-~ ~--. -7": -::,.1c.,....·4--roc'}...eI-·..!ro.--.l- c,.."1'1 .

. ::,~-'~ .J.. 1_ c~~ -;» .. :H .. -G', 9-''"- • ....:..4 - ,..1.', ~~_ a.~.:. ',~~ . ..-_ v. ...:. ,.',_~c.. c:_~ .... ,

SC.7 K.cal!mole of' z i.n c Q::;:~ ,~;lectrica.l 8Dergy."":'l-:.:~ r':~asor.:. ;:',::,=' t:"i::, .:lis-

~:e~~~~~:r~'~d ~~~;;p~!~ei~r~~~ t~f·~ .. :~ ~-r~!~'~~~~1'~;~~~.~;v ~~;i~~~ ~f 3i~~~ ~"tj_~~~

o t~--:~r :forms oi ... e:n.err..:...~:r i. e. el·9ctrical 2T:_C;!_ .... g·:.r? i G a L: .. rp __ ~;TS a c c ~,~:- .. ;_-:::._'.ni e d \)y t~28 tJ:'a::s±-'er- o f 3Gr.:,G r-.:.e2.t· to -:;l~e :3;_::l"'::·o:.:t_rl,jir~,:~;s-~--c:-.:.ly a. fl-'2::.ctir;I: ~)f' heat 9.c,erT.:T( cnt~(!.~lp.z) can he converted i:::,.to (~lectrical e:-:8Tgy.

'_,

, ~ i " .,

2

~' .. .. . .-- \ .,

r':l"lG ce.pa c atiy of' a s y st Gr:! to produce - elect.ricai e~~er~-j" may. be

.... - "f'" /G) . ~ t" t""" - t' -'.. b .

.a s t ne ree c!!.ers:~lT\ .;,." or ra e s y c cm.J...i.'1e r-o i a a o n o nz.p e cw e en

e:;:lGrg-'J.~ch~-:.ge(.3.G2,and pc t.er. t i a L differ<=::cce£~is given b y e

'.

-!0fin8~ :f'ree

/

~ G = .: ' -nFe.

.-;.--

"

. wh e r-e ? is the fflraciay Ln cou.iombs/~o~ of e Le c t r-o.n s ,

n is the numb e r- of::.:oles of e La c t r-o ns tr:~,:n,5i\.=:::::,red· per

r-e ac t an t s', - · ,t

tho uni ts of Uq. will then be joules/mole.

I

mol~ of

.' ;::::818. tionsl:i

b e t we eri En t.h a Lrrv I E j and ?ree ~<:ner

In azry r-e a c t d o n t~~E;re is a t errd ezic y for it to "rno v e " in a dir'.3ctionof-·· lO~.r!er en t ha Lpy and higl'lcr d i, sorder. .rn e di sordqr of ~ syst em is k n o wri

as its entroot{S].If t~e products of a reaction ~re of lowe~ enthalpy

and higher en t r-o py than the r-ea c t azi t s 1 it is easy to see ti!.at the :for-

wa r d .rGaction{reactants ---),products) 1",ill b e s pon t an e ou s Lv a , go on its

own s Eu t if th,e reactal'lts are either,

(i)of 10we;'~nthalPY ~nd lower entropy, or (ii) of' higp~r-:-·r:'>IL't2J.a.lpy and _hi grJ.er. entropy I

,<Jill the for";4irci r".:;actior.. be e po n t a.n e c u s ? "mid: factor, an t ha Lpy OT

cri t r-c py ,.11,1 I aminate? These qu e s t Lori s are ari sv-e r-e d by t:,o e"""'cLoTI

LIlli ::k.:jH - TI.lS ,where Ll G must be negative :for a· e no n t ari e o u s reaction. .! '!

\

than the react~~ts9

,. ,

\ \.

/ \ / :,

, I

t

/

/

. I·.,s..::: ... ;. ~

,I

i

-._

-_

.. - ....

\

-----=-- ..

._----- ----.-----~~---

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