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PHYSICAL

CHEMISTRY II
PROBLEM SET NO. 3

7.4 (a) The mean ionic activity coefficient of 0.1


molal HCl(aq) at 25 C is0.796. What is the activity
of HCl in this solution? (b) The mean activity
coefficient of 0.1 molal H2SO4 (aq) is 0.265. What
is the activity of H2SO4 in this solution?
Given:
HCl:
= 0.796
m = 0.1

H2SO4
= 0.796
m = 0.1

Reqd: (a.) HCl


(b.) H2SO4

PROBLEM SET NO. 3

Solution:
(a.)

HCl H+ + Cl HCl = V m V (v+v+ v-v- )


V= 1 + 1
V = 2
HCl = (0.796) 2 (0.1)2 (11 * 11 )

HCl = 6.34x10-3

PROBLEM SET NO. 3

(b.)
H2SO4 2H+ + SO42-

H2SO4 = V m V (v+v+ v-v- )


V= 1 + 1
V = 2
H2SO4 = (0.265) 3 (0.1)3(22 * 11 )
H2SO4 =7.44x10 -5

PROBLEM SET NO. 3

7.5 The solubility of Ag2CrO4 in water is 8.00 x 10-5


mol kg-1 at 25C, and its solubility in 0.04 mol kg-1
NaNO3 is 8.84 x 10-5 mol kg-1. What is the mean
ionic activity coefficient of Ag2CrO4 in 0.04 mol kg-1
NaNO3?
Solution:
Ksp= Sn
Ksp= solubility of Ag2CrO4 in water
Sn = solubility of Ag2CrO4 in 0.04 mol/kg
= 8.00 x 10-5
8.84 x 10-5
= 0.905
PROBLEM SET NO. 3

7.6 A solution NaCl has an ionic strength of 0.24


mol kg-1 . (a) What is the molality? (b) What
molality of Na2SO4 would have the same ionic
strength? (c) What molality of MgSO4?
Solution:
(a.)
NaCl Na+ + ClI = (m12)+(m12)
I = (m)+(m)
= 2m
I=m
m= 0.24 mol/kg
PROBLEM SET NO. 3

(b.)
Na2SO4 2Na+ + SO4-2

I = (2(m(1)2)+(m(-2)2))
I = (2m+4m)
= (6m)
I = 3m
I/3=m
m= 0.24/3
m= 0.08 mol/kg

PROBLEM SET NO. 3

(c.)
MgSO4 Mg2+ + SO4-2

I = ((m22)+(m(-2)2))
I = (4m+4m)
= (8m)
I = 4m
I/4=m
m= 0.24/4
m= 0.06 mol/kg

PROBLEM SET NO. 3

7.7 Using the limiting law calculate the mean ionic


activity coefficients at 25C in water of the
following electrolytes at 10-3 m: (a) NaCl (b) CaCl2
(c) LaCl3
Solution:
(a) NaCl (1 1) electrolyte
A=0.509
z+= 1
I = m = 10-3
z- = -1
log = Az+z-I1/2
= (0.509)(1)(-1)(10-3)1/2
= 0.964

PROBLEM SET NO. 3

(b) CaCl2 (2 1 electrolyte)


A=0.509
z+= 2
I = 3m = 3(10-3) = 0.003
z- = -1
log = Az+z-I1/2
= (0.509)(2)(-1)(0.003)1/2
= 0.880

PROBLEM SET NO. 3

(c) LaCl3 (3 1 electrolyte)


A=0.509
z+= 3
I = 6m = 6(10-3) = 0.006
z- = -1
log = Az+z-I1/2
= (0.509)(3)(-1)(0.006)1/2
= 0.762

PROBLEM SET NO. 3

7.8 Estimate the cell EMF: Zn(s)|ZnCl2(aq, 0.02


mol kg1)|AgCl(s)|Ag(s)at 25 C the Debye-Huckel
equation.

E = ER - EL
E = 0.222 V (-0.763)
E = 0.985 V
PROBLEM SET NO. 3

By Nernst Equation, we can get the actual cell


potential (EMF)

PROBLEM SET NO. 3

E = 1.140 V

PROBLEM SET NO. 3