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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-:
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 -
- = 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 - |
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 -
!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
b b
2,-2 2,-2
' but 9
.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 .- $as discharged at the anode 6athode solution /y passage of ' mol of electrons ! charges
t- mol of .- ions are lost by transport to the anode ' mol 7+ ions are discharged and thus lost t+ mol 7+ ions are transported into the cathode solution: t+ mol 7+ ions are gained -t+ mol 7+ ions are lost t- mol 7+ ions are
! charges
t+ mol of 7+ ions are lost by transport to the cathode ' mol .- ions are discharged and thus lost t- mol .- ions are transported into the anode solution: t- mol .- ions are gained -t- mol .- ions are lost t+ mol .- ions are lost
6hemistry :'', 0ection ;9, <ecture;' Instructor: 31 != >rner Bhone: :CC: 8ffice: ?@'?A-:
email: fornerD%fupm1edu1sa
<ectures: /uild1 C - 9;'; 073 '':;; - '':C; am 8ffice hours: 073 E:;; - ';:C; in case I am not in office, chec% right outside /uilding ?, maybe I am only C minutes out for smo%ing Fou can also ma%e e4tra appointments for meetings by email or phone -ui,,es: in almost all Gevie$ 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
' .s@&Nm)
force not in vacuum but in a medium $ith relative dielectric constant P &no unit):
"1 " #
#
F=
! o
(=
' &Q@m)@6
&' N.s)@&.sm)
' N@m
electric potential R at distance r from charge - &if the field depends only on distance and not on angles) is defined such that
(=d thus (d = - d d
Integration:
d= = - (d = -
" ! o
d
#
" ! o
The unit is ' N !aradayOs la$ 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
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
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-'
$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+
=
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
-,
(7Ac) = (7/l) + (6aAc) - (6a/l) = (!#-*# + .1*0 - 1#-*0) 5 cm# mol -1 = ,.0*+ 5 cm# mol -1
&b) 6alculate the e#uilibrium constant of acetic acid $ith units in the above solution1 Solution:
8a= c
&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
= 1*00 10 - #
mol , ( 10 -1 m )
= 10*0
mol m
,
)*,10
= #*0! 10 !
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)
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
/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=
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>
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 $hich is also nonsense, because ; t- ' must also be
and to ma%e t+ + t-
mista%e because the students forget that they read their current in m. and not in .
at the cathode a neutral, yello$ 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
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
log10 $+" = - z+ | z- | B I
and in $ater at 9Co6:
I mol 2-1
ionic strength I for ' 7 solutions of different electrolytes: uni-univalent: *a6l *a+&a#) + 6l-&a#)
I=
1 # # # 1 = (1 M (1 + 1 M (-1 )= 1 M ) ) c z i i # # i
summation al$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 #
I=
1 # # # 1 ci zi = (, 1 M (1 ) + 1 M (-, ) ) = - M # i #
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
yu: activity coefficient of the undissociated acid about e#ual to ' because the molecule has no charge ¬ 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
+ # log10 $+" eq eq
u
c 7 + c Acu 8c = c 7Ac
subscript e#: e#uilibrium superscript o: standard state: 9Co6, ' atm, all concentrations e#ual to ' 7 ¬ 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
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
[ 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
/ecause at c
; $e have I
.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
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
= 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
# +"
# # +"
# +"
8 s = a A;+ a/l - = @ A; A
ma4
@ /l - A $+ $ -
I=
.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
+9
8 s = s $+ "
and thus
# #
s=
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
A@ B - A ) = log10 8 o log10 $ s - #
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 #
#
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
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
+" = 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):
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 $ith the electrons cancelling out1 That can be done by 9 4 reduction + o4idation or by reduction + '@9 4 o4idation:
1 7 # (;) + A;/l(s) A;(s) + 7/l(aq) ; z = 1 # 6e nst ' ( = ( o => ln ( a 7 + a/l zF
o4idation
)u =
= (o -
=> => ln( c 7 + c/l - )u ln( + - ) = F F => => u ln( c # ln( +" )# = 7/l ) F F #=> #=> ln mu ln +" F F
= (o -
= (o -
" (+
*ote: superscript u at the molality m of H6l is not a po$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:
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
&mu)'@9
. 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
b=
&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- :t "
= e-1*,)- h
# h
= 0*0-#0
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
.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 # :!
&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 $e get ; on the left hand side and those terms cancel out:
(A) + (B) ' 0 = : 1 @ /7 , /71A - # : ! @ /7 , A # :1 # :!
" @ /7 , A =
@ /7 , /71A
:1 # :!
" @ /7 , /1A =
:# :,
& = : , @ /7 , /1A = : #
C1&.) The density of li#uid mercury at 9A:M is ':1S g cm-: and the surface tension is ;1?A * m-'1 If the contact angle is '?;o, calculate the capillary depression in a tube of ' mm diameter1 Solution:
h ; # cos # cos ;
h=
&/)
If a molecule dissociates on being adsorbed, the process is referred to as dissociative adsorption1 &a) Ierive the <angmuir adsorption isotherm for dissociative adsorption:
= 8@ A# A 1+ 8@ A# A
Solution:
Thus:
adso %tion ' & a = : a @ A# A(1 - )# C action oC C ee sites squa ed "deso %tion ' & d = : d # C action oC occu%ied sites squa ed
: : = a @ A# A = 8@ A# A ; 8 = a # (1 - ) :d :d = 1- "(1 + 8@ A# A ; = 8@ A# A - 8@ A# A
8@ A# A ) =
8@ A# A ; =
8@ A# A 1+ 8@ A# A
&b) Solution:
3hat is the e4pression for the rate of a reaction, assuming that the mechanism of the reaction is unimolecular1 unimolecular reactions on surfaces after
& = := : 1+ 8@ A# A 8@ A# A
dissociation:
&c)
0%etch in the follo$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*,,
, 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:
< #.)*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= ! ,
,
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-:
t+ =
I+ ; = I tI+ + I I+ + I -
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 -
( 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
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 -
!or any strong electrolyte, t+ and t- can be measured for different values of c+
ac and
c-
0ince t+o and t-o can be measured individually, $e can split 5o into
o = +
o ; o= o t + ta b
b b
2,-2 2,-2
' but 9
.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
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