Handouts

Transport numbers to obtain values of mobility u and of ionic molar conductivities for single, individual ions t: transport, transference or migration numbers t+ for a cation; t- for an anion t+ is the fraction of current, I+, carried by the cation total current: I I+ + I-:

I +" t+" = I+ + I t means t+ or t-, and I means the corresponding I+ or I-:

t+ = I+ ; = I tI+ + I I+ + I -

"I = I + + I - ; thus t + + t - = 1 and 0 t +" 1

!or a general electrolyte

+ | |z++ |z -|Aa Bb " a Az+ (aq) + b B z- (aq)

the electro-neutrality condition must hold:

a z+ = b | z - |

in dissociation e#uilibrium for n initial mol of a $ea% electrolyte $e $ill have in solution &'-()n undissociated molecules na( cations and nb( anions transport numbers can be measured for each ion separately *o$, $hat is their relation to mobilities and ionic molar conductivities+ ! is the charge on ' mol of charge, so a mol of a cation $ith charge ,+ have a charge of -+ -a!,+ &for ' mol .a/b) and b!,- &for ' mol .a/b)

0o the electricity flo$ing through a given area . in unit time is a!,+u+ for ' mol .a/b in solution and the negative ion current is b!,-u-, thus
t+ = aF z+ u+ a z + u+ = aF z+ u+ + bF | z - | u - a z+ u+ + b | z - | u " bF | z - | u b | z- | u= t- = aF z+ u+ + bF | z - | u - a z+ u+ + b | z - | u -

and thus t+ + t-

'1

0ince a,+ b2,-2, $e can replace b2,-2 in the denominator of t+ $ith a,+, and a,+ in the denominator of t- $ith b2,-2:

t+ =

a z+ u+ u+ = a z + u + + a z + u - u+ + u -

t- =

b | z- | uu= b | z - | u+ + b | z - | u - u + + u -

3ith the short hand $riting

( Aa Bb ) ; + ( Az++ ) ; - ( B|z-|- )

$e %no$ from before

+ = F z+ u+ ; u+ = +
F z+

- = F | z - | u - ; u - =

F | z- |

= a + + b - = F(a z+ u+ + b | z - | u - )

and therefore
+
t+ = F z+ u+ = + + u+ + u F z+ F | z - |

t- = F | z- | u- = - + u+ + u F z+ F | z - |

*o$ $e can cancel ! and since a,+

z+ =

b2,-2 $e can replace

b 1 a 1 a 1 b 1 | z- | ; = ; | z - | = z+ ; = a b | z - | a z+ z+ b | z - |

and thus

t+ =

a + + z+ = = b + + b a + + b + + a z+ a z +

t- = a + + b | z- | | z- | | z- | =

a + + b

b a + + b -

0ince &see before)

= a + + b thus t + = a + b ; t- =

!or any strong electrolyte, t+ and t- can be measured for different values of c+ ac and cbc and then e4trapolated to t+o and t-o1

0ince t+o and t-o can be measured individually, $e can split 5o into
o ; o= o = t + ta b
o + o o

!or *a6l e1g1 a for 7g8 e1g1 a

b b

' and ,+ ' but ,+

2,-2 2,-2

' but 9

7ethods to measure t+ and tHittorf method

.fter the anode and cathode solutions are connected, a small current is sent through the Hittorf cell for a period of time1 Then the connection is closed, and the anode and cathode solutions after electrolysis can be collected separately and undergo chemical analysis, $hich yields the concentration changes1 !or simplicity let us assume 7+.- electrolytes &can be done for 7a.b ones also, but one has to care then for a and b) cation current fraction: t+ anion current fraction: t-

.fter passing of ' mol electrons through the cell, ! charges have passed through thus !t+ charges are transported to the - electrode &cathode) by 7+ ions and !t- charges are transported to the + electrode &anode) by .ions and because ' mol of charge has passed: ' mol of 7+ $as discharged at the cathode and ' mol of .- $as discharged at the anode 6athode solution /y passage of ' mol of electrons ! charges

t- mol of .- ions are lost by transport to the anode ' mol 7+ ions are discharged and thus lost t+ mol 7+ ions are transported into the cathode solution: t+ mol 7+ ions are gained -t+ mol 7+ ions are lost t- mol 7+ ions are

together &' - t+) mol 7+ ions are lost lost

thus t- mol 7. are lost in the cathode solution .node solution

/y passage of ' mol of electrons

! charges

t+ mol of 7+ ions are lost by transport to the cathode ' mol .- ions are discharged and thus lost t- mol .- ions are transported into the anode solution: t- mol .- ions are gained -t- mol .- ions are lost t+ mol .- ions are lost

together &' - t-) mol .- ions are lost

thus t+ mol 7. are lost in the anode solution:

amount MA lost in anode solution = t+ amount MA lost in cathode solution t = 1 - tt+ = 1 - t+ t-

6hemistry :'', 0ection ;9, <ecture;' Instructor: 31 != >rner Bhone: :CC: 8ffice: ?@'?A-:

email: fornerD%fupm1edu1sa

<ectures: /uild1 C - 9;'; 073 '':;; - '':C; am 8ffice hours: 073 E:;; - ';:C; in case I am not in office, chec% right outside /uilding ?, maybe I am only C minutes out for smo%ing Fou can also ma%e e4tra appointments for meetings by email or phone -ui,,es: in almost all Gevie$ lectures, others $ill be announced about ' $ee% before Hne4cused absence in a #ui,: ; out of ';, no ma%eup Home$or% is assigned but $ill not be collected1 Ho$ever, if you solve the home$or% you can get good grades in -ui,,es &$ill be home$or% problems only) -ui,,es &out of ';;) $ill be averaged to AC each une4cused absence &e4cuses from student affairs must be in ' $ee% after the absence): -' point from class$or%; E une4cused absences: I*

7aJor dates, grading of the course, reading assignments: see syllabus 0ections $hich are not in the syllabus are not covered in class and are not part of e4ams 8vervie$ Klectrochemistry 6hapter A : 0olutions of electrolytes &electrolysis) 6hapter L : Klectrochemical cells &batteries) '1 7aJor K4am 6hemical Minetics 6hapter E : Klementary &one-step) reactions 6hapter '; : Minetics and mechanisms of composite reactions, e1g1: 0tep &') : .+/6 0tep &9) : 6+IK 8verall &6 cancels) : .+/+IK 91 7aJor K4am 0urface 6hemistry 6hapter 'L : .dsorption and adsorption isotherms, heterogeneous catalysis Transport Broperties 6hapter 'E : Niscosity of gases and li#uids and diffusion !inal K4am: 6hapters A,L,E,';,'L,'E &comprehensive) K<K6TG86HK7I0TGF &0olutions of electrolytes) 8bJectives general introduction, !aradayOs la$ of electrolysis, 7olar conductivity 3e are concerned $ith '1 Broperties, li%e conductivity or dissociation of electrolytes in solutions Klectrolyte: a compound that dissociates into ions $hen it is dissolved, e1g1 in $ater or other solvents 91 Brocesses that happen at electrodes $hen immersed in electrolyte solutions Informations can be obtained by the investigation of electrical effects in solutions 7easurement of conductivity versus concentration yields: e4tent of ioni,ation &e1g1 in $ater)

association of ions in solutions &movement of ions bound close together) movement of ions in the solvent &mostly $ater) /asic concepts for electricity Klectrical units Klectrostatic force bet$een 9 charges &unit .s) -' and -9 at distance r:

F=
true in vacuum only

"1 " # ! o #

Po: permittivity or dielectric constant of the vacuum: L1LC? 4 ';-'9 69Q-'m-' '6 ' .s; ' Q ' *m ' %gm9@s9 ' .9s9@&N.sm) ' N.s

Thus ' 69Q-'m-'

' .s@&Nm)

force not in vacuum but in a medium $ith relative dielectric constant P &no unit):
"1 " #
#

F=

! o

= o ' elati&e %e mitti&it$

Klectric field: force@unit charge electric field of charge - at distance r:

" ! o
#

(=

unit: ' *@6

' &Q@m)@6

&' N.s)@&.sm)

' N@m

electric potential R at distance r from charge - &if the field depends only on distance and not on angles) is defined such that
(=d thus (d = - d d

Integration:

 d= = - (d = -

" ! o

d
#

" ! o

The unit is ' N !aradayOs la$ of electrolysis '1 la$: the mass of the element produced &deposited) at an electrode is proportional to the amount of electricity &charge) passed through the solution, $here It; unit: ' .s ' 6 &6oulomb)

91 la$: the mass of the element produced &deposited) at an electrode is proportional to the e#uivalent $eight of the element 7+ + e- 7: e#uivalent $eight 79+ + 9e- 7: e#uivalent $eight charge of ' electron: '1S;9 4 ';-'E 6 charge of ' mol of electrons: '1S;9 4 ';-'E 6 4 *. &.vogadrosOs number) '1S;9 4 ';-'E 6 4 S1;99 4 ';9: mol-' &!aradayOs constant) .g+ + e- .g H+ + e- '@9 H9 Thus a charge of ES?A9 6 produces ' mol .g, but '@9 mol H9 Klectrolysis: the negative electrode attracts cations and is called cathode the positive electrode attracts anions and is called anode /atteries: the negative electrode produces electrons and is called anode ES?A9 6@mol ! molar $eight '@9 molar $eight

the positive electrode ta%es up electrons and is called cathode . solution of gold &III) nitrate, .u&*8:): is electroli,ed using a current of ;1;9C; . until '19; g .u &molar mass 77 'EA1; g@mol) is deposited at the cathode1 '1 3hat is the amount of electricity &charge) passed through the solution+ .u:+ + :e- .u e#uivalent to '@: .u:+ + e- '@: .u ' mol e- yields '@: mol .u ES?A9 6 of charge yield '@: mol .u moles of .u deposited: &'19; g .u)@&'EA1; g@mol) S1;E' 4 ';-: mol .u
1 mol e = 1)*#+ 10 -, mol e 1 mol Au ,

-*0.1 10 -, mol Au

7ultiply by !aradayOs constant to get the charge:

" = .-!+# / 1)*#+ 10 -, mol = 1*+- 10, / (As) mol

91 3hat is the time needed for that+ It and thus the time is t -@I:
t= 1*+- 10 , As = +*0! 10 ! s 0*0#00 A = 1*1+ 10 , min = 1.*- h

:1 The anode reaction is 9 H98 89 + ?H+ + ?e9 o4ygen atoms are o4idi,ed from o4idation number -9 in $ater to ; in o4ygen, and thus ?e - are released1 Iivided by ? the e#uation for ' e- is: '@9 H98 '@? 89 + H+ + eHo$ much &volume) of 89 gas is obtained at 0TB &;o6, ' atm) + ' mol e- '@? mol 89 and thus $e have
1 mol 1 # 1)*#+ 10 - , mol e! mol e = !*0+ 10 -, mol 1 #

The molar volume of 89 at 0TB can be obtained from the ideal gas e#uation BN m atm, T 9A:1'C M and n ' mol and is Nm 991? <@mol &' < ' dm:) and thus
3 1# = ##*! 2 !*0+ 10 -, mol 1 # = 0*10# 2 mol 1 # = 0*10# dm,

nGT at B

'

7olar 6onductivity The nature of solutions can be obtained from conductivity measurements: non-electrolytes: no dissociation into ions, no charge carriers, lo$ conductivity electrolytes: dissociation into ions $hen dissolved, high conductivity t$o types of electrolytes: strong electrolytes: ';;T of the salt is dissociated into ions $hen dissolved, e1g1 *a6l: *a6l *a+&a#) + 6l-&a#) in the solution &no matter if all dissolves or not) there are no U*a6l moleculesU, only ions $ea% electrolytes: only partially dissociated and there are also electrolyte molecules in the solution not only ions, e1g1 acetic acid 6H:688H &H.c)1 dissociation e#uilibrium: or 6H:688H&a#) V W 6H:688-&a#) + H+&a#) H.c&a#) V W .c-&a#) + H+&a#)

in solution all : species are present measurement of conductivity vs concentration of the solute gives informations 8hmOs la$: resistance G is proportional to the voltage N and inversly proportional to the current strength I &proportional to '@I): G unit of G: ' 8hm ' X conductance Y N@I

' N@. &' [email protected]) ' X-'

'@G; unit ' 0 &0iemens)

3hen the current flo$s through a cell of area . &area of the electrodes) and length l &distance bet$een the electrodes), the conductivity Z is defined as
4= A l ; =4 l A

the conductivity is thus the conductance of a unit cube !or solutions the conductivity is also called the electrolytic conductivity unit: ' 0m-' ' X-'m-'

more common is the use of cm instead of m: ' 0cm-' ' X-'cm-'

1 5 5 5 =1 = 100 -# cm m 10 m

Mohlrausch: definition of the e#uivalent conductivity or also called molar conductivity 5:

=

$here c is the molarity of the electrolyte e4ample: the electrolytic conductivity of ;1' 7 &;1' mol@< ;1' mol@dm:) acetic acid is -? C1: 4 '; X-'cm-', $hat is the molar conductivity+
=

0*, 10 -! -1 cm-1 0*1 mol dm-, "

-1 1 cm-1 = 0*, 10 -, mol ( 10+1 cm )-,

-1 1 cm-1 = 0*, 10 -, -, mol 10 cm-,

# # -1 5 = 0*, cm = 0*, cm mol mol

5&c): in all cases 5 slightly decreases $hen c is increased: more electrolyte larger c and smaller molar conductivity

Y&c), Z&c): in all cases Y and Z increase $hen c is increased: more electrolyte <ecture ;9 The electrolytic conductivity at 9;o6 of '1;; 4 ';-9 7 a#ueous solution of acetic acid &H.c) $as found to be '1S; 4 ';-? 0 cm-'1 0ome 5o values are 5o&H6l) ?9S19 0 cm9 mol-', 5o&*a.c) E'1; 0 cm9 mol-' and 5o&*a6l) '9S1C 0 cm9 mol-'1 &a) 6alculate the degree of ioni,ation of acetic acid1 Solution: larger c more ions larger conductance Y and larger conductivity Z

c = 1*00 10 -# M = 1*00 10 -# mol(10 cm ) = 1*00 10 -0 mol cm-, (7Ac) =

-,

1*-0 10 -! 5 cm-1 = 1-*0 5 cm# mol -1 -0 -, 10 mol cm "

o o o

(7Ac) = (7/l) + (6aAc) - (6a/l) = (!#-*# + .1*0 - 1#-*0) 5 cm# mol -1 = ,.0*+ 5 cm# mol -1

1-*0 = 0*0!0.0 = 0*0!10 ,.0*+

&b) 6alculate the e#uilibrium constant of acetic acid $ith units in the above solution1 Solution:
8a= c

# = 1*00 - # M 0*0!0.0# 10 (1 - ) 1 - 0*0!0.0

= 1*+0 10 -0 M

&c) 3hat is the vanOt Hoff factor and the osmotic pressure of this solution+ Solution: v is the theoretical number of particles per dissolved molecule in the solution, if all molecules of H.c $ould dissociate &this is not really the case, so theoretical number)1 0ince H.c, if all molecules $ould dissociate, $ould yield H + and .c-, and thus v molecule1 9 ions per

3hen the degree of dissociation is (, then in solution $e have for each dissolved molecule &' - () undissociated molecules and v( ions1 Thus the vanOt Hoff factor is:
i = 1 - + & = 1 - 0*0!10 + # 0*0!10 = 1*0!10

The concentration is in mol@< and must be changed to mol@m::

c = 1*00 10 - # mol dm
,

= 1*00 10 - #

mol , ( 10 -1 m )

= 10*0

mol m
,

and the osmotic pressure [ is

= ic=> = 1*0!10 10*0 mol m

,

)*,10

< #.,*10 8 8 mol

= #*0! 10 !

:; = #*0! 10 ! 9a = 0*#0! ba m s# = 0*#01 atm

units:
1 9a = 1 6 m
#

=1

:; m s#

= 10-0 ba =

1 atm 1*01,#0 10 0

<ecture ;:? .lternating 6urrents &.6) 6oncept of ionic atmosphere moving together $ith the ions: molar conductivity 5 depends on the fre#uency of an alternating potential If the fre#uency is large enough &very fast change of direction of move) i1e1 so large, that the oscillation time is smaller &faster) than the rela4ation time of the ionic atmosphere: then the ions are stationary and the atmosphere stays symmetric The rela4ation and electrophoretic effects, $hich cause 5 to decrease $ith increasing concentration c, vanish at large .6 fre#uencies Thus at large .6 fre#uencies 5 increases $ith increasing c &more ions charge carriers at higher c)

3ien effect large potentials of about 9;;;; N@cm or larger result in a high speed of the ions Thus the ions move so fast, that the ionic atmosphere cannot follo$ them Thus at very large potentials 5 also increases $ith increasing c,

because the effects from the ionic atmosphere vanish $hen the ions are faster than the atmospheres Iissociation fields $ea% electrolytes in large fields &potentials): 5 becomes large and $ea% electrolytes behave li%e strong electrolytes because the large potentials force the dissolved, undissociated molecules in solutions of $ea% electrolytes to dissociate1

lecture ;?: lineari,ed plots, independent migration of ions: mobility and ionic molar conductivity of ions -uestion: $hich %inds of plots must be linear in case of strong and $ea% electrolytes+ Ietermination if an electrolyte is strong or $ea% from linear plots strong electrolytes molar conductivity as function of concentration:
o = -a c

Thus if the electrolyte is a strong one then a plot of 5 versus c must be linear &6orrelation coefficient r9 close to ') the intercept of the straight line gives 5o $hich is a very good value for strong electrolytes, the slope is -a &the constant in the formula)

$ea% electrolytes 8st$aldOs dilution la$ gives

8= c # 1-

The degree of dissociation &fraction of dissociated molecules) is

and thus

c # c # c o 8 = o = = o 1 1( o - ) o - o o
7ultiplication by the total denominator 5o&5o - 5):
8 o ( o - ) = c #
# 8 o - 8 o = c #

Iivision by M5o95:
1 1 c = # o 8 o 1 1 1 = + c # o 8 o

Thus if the elctrolyte is a $ea% one, then a plot of '@5 versus &c5) &6orrelation coefficient r9 close to ') $ith intercept
inte ce%t = 1 o ; thus o = 1 inte ce%t

Z must give a straight line

/ut 5o values for $ea% electrolytes from such plots are not very good1 To obtain correct 5o values in this case the independent migration of ions la$ must be used /ut using intercepts from such plots and the slope gives good M values:
slo%e = = # 8 o 1 inte ce%t 8
# #

8=

inte ce%t slo%e

In general: derivations given in labs can be as%ed in e4ams\\ <ecture ;C Hittorf 6ell n.: number of moles of 7. lost in the anode compartment n6: number of moles of 7. lost in the cathode compartment nT: total number of moles of 7. deposited at the electrodes nT charge passed@!aradayOs constant, if 7+, and .-

charge passed current strength &I) 4 time &t) nT n. + n6 ratio of the transport numbers: t+@t- n.@n6 since t- ' - t+:
t+ = n A ; t+ n/ = (1 - t + ) n A 1 - t + n/ t+ = nA n = A n A + n/ n>

and therefore t+ = nA n ; t- = / It?F It?F

7oving boundary method for e4ample 7+ &can be H+) or .7O+ and .O- must be slo$er than 7+ and .the indicator solution must change colour $hen 7+ and .- arrive in it for e4ample an acid@base indicator if 7+ is H+ and .- is 8H-

. distinct moving boundary is obtained bet$een 7O. and 7. on one side and bet$een 7. and 7.O on the other side because 7O+ is slo$er than 7+ and cannot overta%e it and because .O- is slo$er than .- and cannot overta%e it moved distances from start &a, b): aaO proportional to u+ and bbO proportional to uto ma%e the boundaries visible indicators must be added that change colour $hen 7+ or .- are there

t+ =

a a b b ; t- = a a + b b a a + b b

8ften seen nonsense lab results: t+ :S; $hich is nonsense, because ; t+ ' must be ', t-:CE $hich is also nonsense, because ; t- ' must also be

and to ma%e t+ + t-

mista%e because the students forget that they read their current in m. and not in .

<ab: ' boundary in acid solution + acid base indicator

at the cathode a neutral, yello$ 6d6l9 solution is produced, but the H+ &acid in the solution) ions move faster to the cathode, and the indicator changes colour $hen the H+ ions leave the - in the beginning - acidic solution belo$ boundary: yello$, neutral 6d6l9 solution &H+ ions moved out) above boundary: red &methylorange) acidic solutions &H+ still there) - It charge transported by the H+ ions, ! !aradayOs constant, c %no$n concentration of the acid solution, . diameter of the tube, aaO distance travelled by the boundary in time t:
aa = t+ " FcA

<ecture ;A 6onsider an electrolyte .a/b Then for electroneutrality $e must have a,+ and for ativity coefficients
a+b a b $+" = $+ $-

b2,-2

(a + b) log10 $+" = a log10 $+ + b log10 $ *o$ $e insert the IH<<:

log10 $ i = - z i# B I

to obtain
# (a + b) log10 $+" = - (a z+ + b z -# )B I

# # # a # z+ b z=- + a b

B I

electroneutrality: &b2,-2)9

&a,+)9:
# 1 1 (a + b) log10 $+" = - a# z+ + B I a b

# = - a # z+

a+b B I ab

a # B I log10 $+" = - z+ b

electroneutrality: b2,-2

a,+: a@b

2,-2@,+ and thus

log10 $+" = - z+ | z- | B I
and in $ater at 9Co6:

log10 $+" = - 0*01 z+ | z- |

I mol 2-1

ionic strength I for ' 7 solutions of different electrolytes: uni-univalent: *a6l *a+&a#) + 6l-&a#)

I=

1 # # # 1 = (1 M (1 + 1 M (-1 )= 1 M ) ) c z i i # # i

summation al$ays over .<< ions in a solution uni-bivalent: *a908? 9 *a+&a#) + 08?9-&a#)

I=

1 # # # 1 ci zi = (# 1 M (1 ) + 1 M (-# ) ) = , M # i #

uni-trivalent: *a:B8? : *a+&a#) + B8?:-&a#)

I=

1 # # # 1 ci zi = (, 1 M (1 ) + 1 M (-, ) ) = - M # i #

bi-trivalent: 7g:&B8?)9 : 7g9+&a#) + 9 B8?:-&a#)

I=
<ecture ;L

1 # # # 1 ci zi = (, 1 M (# ) + # M (-, ) ) = 10 M # i #
Ionic e#uilibria

8bJectives: activity coefficients from e#uilibrium constants and solubility products K#uilibrium is obtained very rapidly in ionic solutions e4ample: H.c V W H+ + .cH.c: 6H:688H; .c-: 6H:688activity: a &]) cy activity coefficient is $ritten as english lo$er case y or as gree% lo$er case gamma

The dissociation constant Ma of acetic acid is practically

8a=
a 7 + a Ac- @ 7 + A @ Ac A $+ $ = @7AcA $u a 7Ac

yu: activity coefficient of the undissociated acid about e#ual to ' because the molecule has no charge &not e4actly ' because of the dipole moment) the activity coefficients of cations &y+) and of anions &y-) are not ', because of the charges and their interactions mean activity coefficient y for ./ compunds: y &y+y-)'@9; &y)9 y+yfor .a/b compounds: &y)a+b Therefore &y+)a&y-)b

@ 7 + A@ Ac- A # $+" 8a= @7AcA

ta%ing logarithm basis '; gives
c 7 + c Aclog10 8 = log10 c 7Ac
u a

+ # log10 $+" eq eq
u

c 7 + c Acu 8c = c 7Ac

superscript u: units ta%en out

subscript e#: e#uilibrium superscript o: standard state: 9Co6, ' atm, all concentrations e#ual to ' 7 &not e#uilibrium)1 so superscript o at an e#uilibrium constant means only 9Co6, ' atm Thus

c 7 + c Aclog10 c 7Ac

u = log10 8 a - # log10 $ eq

= - %8 a - # log10 $+"
8st$aldOs dilution la$:

c 7 + c Ac c 7Ac
Thus

# ; = = c 1- o eq

c # = log10 8 u log10 a - # log10 $ 1 - eq

8n the left and right hand side the same unit must be ta%en out &mol@<) IH<<:
c # u log10 1- = log10 8 a + # z+ | z - | B I eq
u

;1C' dm:@9mol'@9 in $ater at 9Co6

I= 1 # c
i i # z i ; c 7 + = cB c Ac- = c

" c 7Ac = c(1 - ) (no ion) I= 1 #

[ c1

+ c1# ] = c

if there are no other ions present, $hich in case must be added to I1 Thus one has to measure 5 at different concentrations c and obtain 5o1 Then one can calculate ionic strength for each c value and

 # c u o c # log10 1- = log10 1 o

*o$, at small c values only a plot of this #uantity versus s#uare root of the ionic strength I '@9 $ill give a straight line $here c is small enough that IH<< is obeyed1 The straight line at small I &c) has the slope 9/ $hen ,+2,-2 9/ '1;9 dm:@9 mol'@9 at 9Co6 and ' atm, Mu is also $ritten as Mo &$ithout units) 3hen I and thus c goes to ;, then the e#uation tells
c # log10 1 - o = log10 8
u

' as in our case and in $ater at 9Co6:

/ecause at c

; $e have I

; and according to IH<< y

' and thus log';y

.t larger I &larger c) $here IH<< is not obeyed &no straight line) the difference bet$een the measured points and log';Mo is e#ual to -9log';y and the mean activity coefficient can be obtained at all c values, since

c # - # log10 $+" = log10 - log10 8 o 1-

values of y+ or y- cannot be obtained, only the mean value by plotting
c # C = log10 1- &e sus
u

3hen I is very small, the plot can also be done as f versus m &molality) 0olubility products The solubility product Ms is a constant in saturated &as much electrolyte is dissolved as possible) solutions of electrolytes1 K4ample: .g6l V W .g+&a#) + 6l-&a#) The largest amount of .g6l that can be dissolved is the solubility s: s ^.g6l_ma4 ^.g+_ma4 ^6l-_ma4 and

+ ma4 - ma4 + = = @ @ 8 s a A; a/l A; A /l A $+ $-

= s s $ = s $ since $ = $+ $K4ample: Bb6l9 V W Bb9+&a#) + 9 6l-&a#) The largest amount of Bb6l9 that can be dissolved is the solubility s: s ^Bb6l9_ma4 ^6l-_ma4 9s ^Bb9+_ma4 '@9 ^6l-_ma4 and thus

# +"

# # +"

# +"

# # #+ ma4 - ma4 # # + = = @ (@ ) $ $ A A /l 8 s a9b a/l- 9b + -

= s (#s )# $+, " = ! s, $+, " since $+, " = $+ $-#

.dding of an inert electrolyte .n electrolyte inert to .g6l is one that has no ions that are also in .g6l *a/r is inert to .g6l since it has no .g+ or 6l- ions *a6l is non-inert to .g6l because it has 6l- ions as also .g6l then ^6l-_ from *a6l is much larger than ^6l-_ma4 from .g6l and

8 s = a A;+ a/l - = @ A; A

ma4

@ /l - A $+ $ -

# - 6a/l # = s (s + @ /l - A 6a/l ) $+ $+" " s@ /l A

since @ /l - A 6a/l much la ;e than s

adding of an inert electrolyte brings about no chemical change, but it changes y because it changes I: no inert *a/r:
1 1 # # (@ A; + A ma4 z+ + @ /l - A ma4 z ) = (s 1# + s 1# ) = s # #

I=

inert *a/r present:

I= 1 (@ A; + A ma4 1# + @ /l - A ma4 1# + @ 6a+ A 1# + @ B - A 1# ) # = 1 (#s + #@6aB A) = s + @6aB A #

.t lo$ I IH<< &at higher I the 6I correction must be added) is valid IH<<:

log10 $+" = - z+ | z- | B I
Thus, $hen I increases because of adding an electrolyte, then the activity coefficients drops &becomes smaller) because of the - sign, $hen I is so small that IH<< holds at high I log';y increases $hen I increases, can even become positive, because the 6I correction &positive) must be added lo$ I y decreases $ith increasing I, but Ms must be a constant:

## = 8 s s $+" = constant
3hen Ms must be the same, then $hen y decreases, s must increase thus more .g6l goes into solution than into pure $ater $hen *a/r is added to it: salting in effect large I y increases $ith increasing I, but Ms must be a constant:

## = 8 s s $+" = constant
3hen Ms must be the same, then $hen y increases, s must decrease thus less .g6l goes into solution than into pure $ater $hen *a/r is added to it: salting out effect K4ample: Ms&/a08?) E19 4 ';-'' 79 &mol9@<9 mol9@dmS)

3hat is y in a solution &in $ater at 9C o6) that is saturated in /a08? and contains also ;1;C 7 M*8: and ;1;C 7 M6l, salting in or salting out effect+ assume that IH<< applies In the solution $e can neglect the /a9+ and 08?9- concentrations because they are much smaller than those of M*8: and M6l:
I= 1 # (@ 8 + A 861, 1# + @ 61 , A 1 + # + @ 8 + A 8/l 1# + @ /l - A 1# ) = 1 (0*00 + 0*00 + 0*00 + 0*00) M = 0*1 M #

IH<<:
log10 $+" = - z+ | z - | B I = - # # 0*01 = - 0*-!0 $+" = 10-0*-!0 = 0*##2 mol 0*1 mol 2

note that for /a08? ,+ +9 and ,The solubility product is

-9, thus 2,-2

+9

8 s = s $+ "
and thus

# #

s=

8s = !*#! 10-0 M $+"

In pure $ater s is so small that I is almost ; and thus y is almost ':

# 8 s = s thus s = -8 s = .*- 10 M

In the M*8:@M6l solution more /a08? is dissolved than in pure $ater: salting in effect If for a salt Ms is larger, i1e1 ';-: or so, the above is only the first step in an iteration: use the solubility to calculate a ne$ I, a ne$ y and a ne$ solubility1 Gepeat until there is no more change salting out happens only $hen I is so large that the 6I correction becomes important and

log10 $+" = -

z+ | z - | B I + /I 1 + aB I

6onsider a simple ./ electrolyte: ./&s) V W .+&a#) + /-&a#), then

+ + a B- = @ A A@ B A $+ $ - = @ A A@ B A $+ " 8 s = a a+ #

+ A@ B - A )u + # log10 8 o log10 $+ " s = log10 (@ A

" log10 (@A A

+

A@ B - A ) = log10 8 o log10 $ s - #

In a saturated solution that contains only ./ and inert electrolytes $e have

s = @ A+ (aq) A ma4 = @ B - (aq) A ma4 = @AB(aq) A ma4

and thus
log10 ( s u ) = log10 8 o s - # log10 $+ " ; = log10 su = 1 log10 8 o s - log10 $ # 1 I log10 8 o s + B #
#

D722 ' ; = log10 su =

Blot as before g log';su versus I'@9 then at lo$ I &IH<<) a straight line $ith slope / &;1C' < '@9mol-'@9 in $ater at 9Co6) is obtained and its intercept is ;1C 4 log';Mso1

since

1 1 - log10 $+" = ; - log10 8 os = log10 su - log10 8 os # #

Lecture 45: '1 Final Exam from May, 1999 The solubility product of /a08? is E19 4 ';-'' mol9dm-S1 &a) 6alculate the mean activity coefficient of the /a9+ and 08?9- ions in a solution in $ater at 9Co6, that is ;1;C 7 in *a*8: and ;1;C 7 in M6l, assuming the IH<< to apply1 Solution IH<<:

log10 + " = - 0*01 z+ | z - |

I M -1 ; z+ | z - |= + # | -# | = !

ionic st en;th ' 1 0*00 M 1# ( 6a+ ) + 0*00M (-1 )# ( 61 , )+ # + 0*00M 1# ( 8 + ) + 0*00M (-1 )# ( /l - ) = 1 ! 0*00 M = 0*10 M #

I=

0ince the concentrations of /a9+ and 08?9- ions are about the s#uare root of the solubility product, and therefore about ';-C to ';-? 7, they can be neglected as compared to ;1;C 71 Then

log10 +" = - 0*01 ! 0*1 = - 0*-!0

+" = 10-0*-!0 = 0*##&b) Solution 3hat is the solubility of /a08? in that solution, and The constant solubility product implies that the concentrations of /a 9+ and 08?9- in there are actually each one e#ual to the solubility of /a08? &saturated solution):

# # # + # # + # = = = 8 s% aBa a51! cBa + c51! - s +"

*ote: the above is true only for ./ electrolytes1

8 s% .*# 10-11 M # s= = = !*#! 10-0 M 0*## +"

&c) Solution: in pure $ater+ 0ince in pure $ater the ionic strength contains only the terms for the /a9+ and for the 08?9- ions, $hich are very small due to the small Msp, $e can appro4imate I by ;:

I 0 " log10 +" 0 " +" 1 " 8 s% = s# +# " s# " s = 8 s% = .*0. 10-- M
The fact that more /a08? dissolves in *a*8:@M6l solution than in pure $ater is called "salting in" effect1

91

The cell Bt&s), H9 &' bar) 2 H6l &m) 2 .g6l&s) 2 .g&s) gives the follo$ing emf values at 9Co6: m@&mol %g-') K@N &K + &9GT@!) ln mu )@N """""""""""""""""""""""""""""""""""""""""" :19'C 4 ';-: ;1C9;; ?1?LL 4 ';-: ;1C;:E C1S'E 4 ';-: ;1?E:: -: A1:'' 4 '; ;1?L'9 """""""""""""""""""""""""""""""""""""""""" &a) 3hat is the cell reaction+ right side: reduction

Solution

.g6l&s) + e- .g&s) + 6l-&a#) left side : H9&g) 9H+&a#) + 9eThe cell reaction is the sum of the t$o $ith the electrons cancelling out1 That can be done by 9 4 reduction + o4idation or by reduction + '@9 4 o4idation:
1 7 # (;) + A;/l(s) A;(s) + 7/l(aq) ; z = 1 # 6e nst ' ( = ( o => ln ( a 7 + a/l zF

o4idation

)u =

= (o -

=> => ln( c 7 + c/l - )u ln( + - ) = F F => => u ln( c # ln( +" )# = 7/l ) F F #=> #=> ln mu ln +" F F

= (o -

= (o -

" (+

#=> #=> ln mu = ( o ln +" F F

*ote: superscript u at the molality m of H6l is not a po$er, but means Uremove the unit before ta%ing the lnU1 !urther note, that ^H+_ ^6l-_ ^H6l_ m at all times1

0ince K is positive, the reaction goes in the direction as derived above &if it $ould be reversed, K $ould be negative)1 It can be sho$n that the e4pression for the emf of this cell over a range of concentrations of H6l is given by

(+
&b) Solution:

#=> u o #=> ln m = ( - ln +" F F

6omplete the table above and determine K o on the supplied sheet of graph paper $ith the a4is already mar%ed &plot y versus mu\)1 <inear regression is also acceptable1 Tric : $e define
$ (+ #=> ln mu and E mu F

. plot of y versus 49 could give us a straight line y a49+b $ith slope a and intercept b, $hen such plots are done for small concentrations as here1 /ut $hen 4 is small then ln&'+4) 4 *8T ln4 41 0ince IH<< applies for small concentrations, $e can replace ln by log'; $ith the help of 91:;: and insert the IH<<1 .lso a slope of 9GT@! is not important1 Thus
$ = (o #=> ln +" ; D722 ' log10 +" = - z+ | z - | B I F

"7/2 ' z+ | z - |= 1 ; ln + " = #*,0, log10 + " " $ = (o + #=>B #*,0, I ; 7/l ' I = m F #=>B #*,0, m F

" $ = (o +

Then a plot of y vs I'@9 is a straight line $here IH<< applies1 0ince $ith H6l I ;1C&c&H+)+c&6l-)) m, thus here a plot of y vs m'@9 must give a straight line1 .t the intercept mu is ;1 Thus &here: molality not molarity, thus *8T / ;1C'7-'@9)
$( mu = 0) = b = ( o + #=>B #*,0, m = ( o " b = ( o F

6ompleted table &9GT@! m &';-: mol@%g) :19'C ?1?LL C1S'E A1:'' K&N) ;1C9;; ;1C;:E ;1?E:: ;1?L'9

C1':LE 4 ';-9 N):

y K + &9GT@!)ln mu &N) ;199C; ;199S' ;199A; ;199L?

m &';-: mol@%g) :19'C ?1?LL C1S'E A1:''

ln mu -C1A:EE -C1?;S: -C1'L'S -?1E'L?

&mu)'@9

;1;CSA;' ;1;SSEE: ;1;A?ES; ;1;LCC;?

. plot y vs mu, assuming 4'@9 4 for small 4, is not that good, cause a Taylor series of 4 '@9 around 4 ; is not possible1 In linear regression $e have

a=

6 Ei $i - ( Ei )( $i )
i i i

D
b=
i i

; D= 6 E -( E )
# i i i i

( Ei# )( $i ) - ( Ei )( Ei $i )
i i

D
;1;9;S::

$here the number of &4i, yi) points * ?1 !rom the table $e get: `yi `4iyi ;1E;SC N `4i ;19L?'S `4i9

;1;S??C; N &note that 4 mu and thus has no units)

D = ! 0*0#0-,, - (0*#)!1- )# = 1*+)01 10 -, a= ! 0*0-!!00 3 - 0*#)!1- 0*.0-0 3 = 0*11+1 3 1*+)01 10 -, 0*0#0-,, 0*.0-0 3 - 0*#)!1- 0*0-!!00 3 = 1*+)01 10 -, = 0*#1), 3 = ( o

b=

0o, our final regression function is

$ = 0*11+1 3 mu + 0*#1), 3

&b) Solution:

6alculate the activity coefficient for a S1;;; 4 ';-: m solution of H6l1 !irst $e need y&;1;;S m) for that concentration:
$(0*00- m) = 0*11+1 3 0*00- + 0*#1), 3 = 0*##+! 3

Then using the right hand side of the above given e#uation $e obtain:

$ = (o -

#=> ln +" F

" $(0*00- m) = 0*#1), 3 - 0*1,). 10 - # 3 ln + " " ln + " = (0*#1), - 0*##+!) 3 = - 0*1++1 0*1,). 10 - # 3

" + " = e-0*1++1 = 0*),++

:1 . solution of . is mi4ed $ith an e#ual volume of a solution of / containing the same number of moles &initial concentrations ao and bo are e#ual) and the reaction .+/6 occurs1 .t the end of ' h, . is !5" reacte#1 Ho$ much of . &in T of the initial concentration ao) $ill be left unreacte# at the end of 9 h, if &a) the reaction is first order in . and ,ero order in /1

d@AA d@AA = - :@AA " = - : dt @AA dt 0 ao ln a ao = - :t

aCte 1 h ' a = #0F ao = 0*#0 ao

ACT of ao has reacted, i1e1 9CT of ao remains unreacted:
ln 0*#0 = - : 1 h " : = a ao a(# h) ao ln 0*#0 = 1*,)- h-1 1h
-1

= e- :t "

= e-1*,)- h

# h

= 0*0-#0

" a = 0*0-#0 ao = -*#0F ao un eacted aCte # h

&b) the reaction is both first order in . and first order in /1

d@AA = - :@AA@BA = - :@A A # cause ao = bo thus a = b at all times dt 1 1 1 1 d@AA dt " - ( - ) = - :t ; :t = @A A # = - : a ao a ao 0 ao " : 1 h= 1 1 1 , - " := (! - 1) = 0*#0 ao ao hao hao
a t

"

1 1 - 1 1 1 + # h= - " = - " = a ao ao a ao a a o hao 1 " a = ao = 0*1!, ao = 1!*,F ao +

?1

.cetaldehyde decomposes thermally and the main products are methane and carbon mono4ide1 . li%ely mechanism is: 6H:6H8 6H: + 6H8 &rate constant %') 6H: + 6H:6H8 6H? + 6H:68 &rate constant %9) 6H:68 68 + 6H: &rate constant %:) 6H: + 6H: 69HS &rate constant %?) Ierive the e4pression for the rate of formation of 68:
d@/1A :1 = :# @ /7 , /71 A ,?# dt # :!

&') &9) &:) &?)

&To simplify the steady state treatment, further reactions of the radical 6H8 have been omitted and their rate e#uations may be ignored) Solution:
&= d@/1A = : , @ /7 , /1A dt

6H:68 is an intermediate $ith un%no$n, small and constant concentration1 It must be obtained from the steady state appro4imation for the t$o intermediates 6H: and 6H:68 in terms of reactant and product concentrations and rate constants1

The reactant is 6H:6H8, main products are 6H? and 68, 69HS is a by-product, 6H8 is also an intermediate radical, but its reactions are neglected:
(A) ' d@ /7 , A = 0 = : 1 @ /7 , /71A - : # @ /7 , A@ /7 , /71A dt - # : ! @ /7 , A # + : , @ /7 , /1A (B) ' d@ /7 , /1A = 0 = : # @ /7 , A@ /7 , /71A - : , @ /7 , /1A dt

*ote that, loo%ing at reaction &?) alone, $e get the follo$ing rate term:
&! = 1 # &/7 , B! = - : ! @ /7 , A #

" &/7 , B! = - # : ! @ /7 , A #

*ote, that the terms at %9 and %: are $ith opposite signs in both e#uations1 Thus $hen $e add the e#uations $e get ; on the left hand side and those terms cancel out:
(A) + (B) ' 0 = : 1 @ /7 , /71A - # : ! @ /7 , A # :1 # :!

" @ /7 , A =

@ /7 , /71A

into (B) ' : #

:1 # :!

@ /7 , /71 @ /7 , /71A - : , @ /7 , /1A = 0

" @ /7 , /1A =

:# :,

:1 @ /7 , /71 A ,?# # :! :1 @ /7 , /71 A ,?# # :!

& = : , @ /7 , /1A = : #

C1&.) The density of li#uid mercury at 9A:M is ':1S g cm-: and the surface tension is ;1?A * m-'1 If the contact angle is '?;o, calculate the capillary depression in a tube of ' mm diameter1 Solution:

h ; # cos # cos ;

h=

# 0*!+ :; s - # cos( 1!0 o ) 0*0 10 -, m 1,*- ( 10 - , :;)( 10 - # m )- , .*)1 m s - # = - 1*0) 10 - # m = - 10*) mm

&/)

If a molecule dissociates on being adsorbed, the process is referred to as dissociative adsorption1 &a) Ierive the <angmuir adsorption isotherm for dissociative adsorption:
= 8@ A# A 1+ 8@ A# A

Solution:

Geaction of ' .9 $ith 9 surface sites: .. 2 2 2 2 .9 + -0-0- -0-0-

Thus:
adso %tion ' & a = : a @ A# A(1 - )# C action oC C ee sites squa ed "deso %tion ' & d = : d # C action oC occu%ied sites squa ed

In e#uilibrium the rates are e#ual:

# # & a = & d " : a @ A# A(1 - ) = : d

: : = a @ A# A = 8@ A# A ; 8 = a # (1 - ) :d :d = 1- "(1 + 8@ A# A ; = 8@ A# A - 8@ A# A

8@ A# A ) =

8@ A# A ; =

8@ A# A 1+ 8@ A# A

&b) Solution:

3hat is the e4pression for the rate of a reaction, assuming that the mechanism of the reaction is unimolecular1 unimolecular reactions on surfaces after
& = := : 1+ 8@ A# A 8@ A# A

dissociation:

&c)

0%etch in the follo$ing graph the variation of the rate $ith ^.9_'@91

Solution:

&d) 3hat $ould be the order of the reaction, $hen &i) lo$

^.9_ is

Solution:
8@ A# A G 1 " & = : 8@ A# A ' o de 1 #

&ii) Solution:

high
: 8@ A# A 8@ A# A

8@ A# A H 1 " & =

= : ' o de 0

S1

&a)

In a normal adult at rest the average speed of flo$ of blood through the aorta is ;1:: m s-'1 The radius of the aorta is E mm and the viscosity of blood at body temperature , :Ao6, is about ?1; 4 ';-: %g m-' s-'1 &i) 6alculate the rate of flo$ of blood through the aorta1

Solution:
a ea ' A =
#

= ,*1!1- (. 10 -, )# m #

= #*0! 10 -! m # ate oC &olume CloI = a&e a;e s%eed a ea A

" = 0*,,
, m d3 #*0! 10 - ! m # = )*!0 10- 0 m = s s dt

&ii) 6alculate the pressure drop along ;1C m length of the aorta1 Solution: Bouisseuille e#uation:
d3 ! 9 )l d3 = ; 9 = dt )l ! dt " :; ) !*0 10 -, 0*0 m , -0 m ms 9 = )*! 10 ! s ,*1!1- (. 10 -, ) m! = -0*# 9a 1 >o = 0*!. >o 1,,*,## 9a

&b)

The diffusion coefficient for glucose in $ater is S1L' 4 '; -'; m9 s-' at 9Co61 The viscosity of $ater at 9Co6 is L1E:A 4 ';-? %g m-' s-' and the density of glucose is '1CC g cm-:1 .ssume the glucose molecule to be spherical and to obey 0to%esOs la$1 &i) Kstimate the radius of a glucose molecule1

Solution:

5 to:ess laI ' D =

:B> : > " = B - -D

< #.)*10 8 8 = # :; - ,*1!1- -*)1 10 -10 m )*.,+ 10 -! s ms 1*,)1 10 - #, = 0*,0. 10 -. <m = 0*,0. nm :; m# s
#

&ii) Kstimate the molar mass of glucose1 Solution: The radius of a spherical molecule gives the volume of ' molecule:
3= ! ,
,

! ,*1!1- (,*0. 10 -. ), m, = 1*.,) 10 - #) m, ,

The density and the volume give the mass of ' molecule:
-, :; m = 3 = 1*00 10- # 1*.,) 10 - #) m, = ,*00 10 - #0 :; ( 10 m ),

The mass of ' molecule and .vogadroOs number give the molar mass 77:
MM = m 6 A = ,*00 10 -## ; -*0## 10 #, mol -1 = 1)0*+ ; mol -1

Transport numbers to obtain values of mobility u and of ionic molar conductivities for single, individual ions t: transport, transference or migration numbers t+ for a cation; t- for an anion t+ is the fraction of current, I+, carried by the cation total current: I I+ + I-:

I +" t+" = I+ + I t means t+ or t-, and I means the corresponding I+ or I-:

t+ =

I+ ; = I tI+ + I I+ + I -

"I = I + + I - ; thus t + + t - = 1 and 0 t +" 1

!or a general electrolyte
+ | |z++ |z -|Aa Bb " a Az+ (aq) + b B z- (aq)

the electro-neutrality condition must hold:

a z+ = b | z - |

in dissociation e#uilibrium for n initial mol of a $ea% electrolyte $e $ill have in solution &'-()n undissociated molecules na( cations and nb( anions transport numbers can be measured for each ion separately *o$, $hat is their relation to mobilities and ionic molar conductivities+ ! is the charge on ' mol of charge, so a mol of a cation $ith charge ,+ have a charge of -+ -a!,+ &for ' mol .a/b) and b!,- &for ' mol .a/b)

0o the electricity flo$ing through a given area . in unit time is a!, +u+ for ' mol .a/b in solution and the negative ion current is b!,-u-, thus
t+ = aF z+ u+ a z + u+ = aF z+ u+ + bF | z - | u - a z+ u+ + b | z - | u " bF | z - | u b | z- | u= t- = aF z+ u+ + bF | z - | u - a z+ u+ + b | z - | u -

and thus t+ + t-

'1

0ince a,+ b2,-2, $e can replace b2,-2 in the denominator of t+ $ith a,+, and a,+ in the denominator of t- $ith b2,-2:
t+ = a z+ u+ = u+ a z + u + + a z + u - u+ + u -

t- =

b | z- | uu= b | z - | u+ + b | z - | u - u + + u -

3ith the short hand $riting

( Aa Bb ) ; + ( Az++ ) ; - ( B|z-|- )
$e %no$ from before
+ = F z+ u+ ; u+ = +
F z+

- = F | z - | u - ; u - =

F | z- |

= a + + b - = F(a z+ u+ + b | z - | u - )

and therefore

+
t+ = F z+ u+ = + + u+ + u F z+ F | z - |

t- = F | z- | u- = - + u+ + u F z+ F | z - |
b2,-2 $e can replace

*o$ $e can cancel ! and since a,+

z+ =

b 1 a 1 a 1 b 1 | z- | ; = ; | z - | = z+ ; = a b | z - | a z+ z+ b | z - |

and thus

t+ =

a + + z+ = = b + + b a + + b + + a z+ a z +

t- = a + + b | z- | | z- | | z- | =

a + + b

b a + + b -

0ince &see before)

= a + + b thus t + = a + b ; t- =

!or any strong electrolyte, t+ and t- can be measured for different values of c+

ac and

c-

bc and then e4trapolated to t+o and t-o1

0ince t+o and t-o can be measured individually, $e can split 5o into
o = +

o ; o= o t + ta b

!or *a6l e1g1 a for 7g8 e1g1 a

b b

' and ,+ ' but ,+

2,-2 2,-2

' but 9

7ethods to measure t+ and tHittorf method

.fter the anode and cathode solutions are connected, a small current is sent through the Hittorf cell for a period of time1 Then the connection is closed, and the anode and cathode solutions after electrolysis can be collected separately and undergo chemical analysis, $hich yields the concentration changes1 !or simplicity let us assume 7+.- electrolytes &can be done for 7a.b ones also, but one has to care then for a and b) cation current fraction: t+ anion current fraction: t.fter passing of ' mol electrons through the cell, ! charges have passed through thus

!t+ charges are transported to the - electrode &cathode) by 7+ ions and !t- charges are transported to the + electrode &anode) by .- ions and because ' mol of charge has passed: ' mol of 7+ $as discharged at the cathode and ' mol of .- $as discharged at the anode 6athode solution /y passage of ' mol of electrons ! charges

t- mol of .- ions are lost by transport to the anode ' mol 7+ ions are discharged and thus lost t+ mol 7+ ions are transported into the cathode solution: t+ mol 7+ ions are gained -t+ mol 7+ ions are lost t- mol 7+ ions are lost

together &' - t+) mol 7+ ions are lost

thus t- mol 7. are lost in the cathode solution .node solution /y passage of ' mol of electrons ! charges

t+ mol of 7+ ions are lost by transport to the cathode ' mol .- ions are discharged and thus lost t- mol .- ions are transported into the anode solution: t- mol .- ions are gained -t- mol .- ions are lost t+ mol .- ions are lost

together &' - t-) mol .- ions are lost

thus t+ mol 7. are lost in the anode solution:

amount MA lost in anode solution = t+ amount MA lost in cathode solution t = 1 - tt+ = 1 - t+ t-