Yerro, Jennylyn Z.

Jan. 13, 2012

2009-23621

MM-003

Solution:

A determination of the transference numbers of cadmium and iodide ions by

Hittorf gave the following data: A stock solution of CdI 2 was prepared, and its
concentration was determined, by precipitation of iodide as AgI, to be 0.002763g
of CdI2 per gram of solution. Another sample of this solution was placed in a
Hittorf transference-number cell, and current was passed through the cell. It was
found out that 0.03462g cadmium was deposited at the cathode by the passage
of the current. Furthermore, analysis of the anode compartment solution, which
weighed 152.643g, indicated the presence of 0.3718g of cadmium iodide. (a)
What are the electrode reactions? (b) How many coulombs of charge were
passed through the cell in the experiment? (c) What are the transference
numbers of Cd2+ and I- in the solution? (d) What was the change in the
equivalents of CdI2 in the cathode compartment?

Molar conductivity (S cm2 mol-1) data at 18oC and varying concentration are

MM-006
given:

c, M
0.00100
0.0100
0.100
, (NH4NO3)
124.25
118.00
106.60
, (KOH)
234.0
228.0
213.0
, (KNO3)
123.7
118.2
104.8
From these data calculate the limiting molar conductivity of NH4OH. If = 28, 9.6,
3.3 S cm2 mol-1 at 0.001, 0.01 and 0.1M, respectively, what is its degree of
ionization () at these concentrations?
Solution:
NH4NO3 + KOH KNO3 + NH4OH
0M NH4OH = (NH4+) + (OH-)
= 0M (KOH) + 0M (NH4NO3) - 0M (KNO3)
1/ M = 1/ 0M + CM/Ka(0M)2
1/ M =[ 1/Ka(0M)2]x CM + 1/ 0M resembles the linear equation y=mx + b
So y (1/ M) vs. x (CM) was plotted.
A plot of 1/ M vs. C M for each species.
For NH4NO3:
(NH4NO3)
124.25
118
106.6

1/M
0.00804829
0.008474576
0.009380863

c
0.001
0.01
0.1

CM
0.12425
1.18
10.66

1/M vs. CM(NH4NO3)

0.0096
y = 0.0001143x + 0.0081789
R = 0.9491521

0.0094
0.0092
1/M

0.009
0.0088
0.0086
0.0084
0.0082
0.008
0.0078
0

6
CM

10

12

For KOH:
(KOH)

1/M
c
234 0.004273504
228 0.004385965
213 0.004694836

CM
0.001
0.234
0.01
2.28
0.1
21.3

1/M

1/M vs. CM(KOH)

0.00475
0.0047
0.00465
0.0046
0.00455
0.0045
0.00445
0.0044
0.00435
0.0043
0.00425

y = 0.0000185x + 0.0043046
R = 0.9705334

10

15

20

25

CM

For KNO3:
(KNO3)
123.7
118.2
104.8

1/M
c
0.008084074
0.008460237
0.009541985

CM
0.001
0.01
0.1

0.1237
1.182
10.48

1/M vs. CM(KNO3)

0.0098

y = 0.0001312x + 0.0081801
R = 0.9752017

0.0096
0.0094

1/M

0.0092
0.009
0.0088
0.0086
0.0084
0.0082
0.008
0

6
CM

The equations of the line for the three species are:

10

12

 NH4NO3: y = 0.0001143x + 0.0081789

KOH: y = 0.0000185x + 0.0043046
KNO3: y = 0.0001312x + 0.0081801
To get for the 0M:
y-intercept, b, of each equation of the line corresponds to 1/ 0M. (0M= 1/b)
For NH4NO3: y = 0.0001143x + 0.0081789
0M= 1/b =1/0.0081789
0M= 122. 266 S cm-2 mol-1
For KOH: y = 0.0000185x + 0.0043046
0M= 1/b =1/0.0043046
0M= 232.310 S cm-2 mol-1
For KNO3: y = 0.0001312x + 0.0081801
0M= 1/b =1/0.0081801
0M= 122.248 S cm-2 mol-1
0M NH4OH = 0M (KOH) + 0M (NH4NO3) - 0M (KNO3)
= 122.266 + 232.310 - 122.248
0M= 232.328 S cm-2 mol-1
0M NH4OH = 232.328 S cm-2 mol-1
Degree of ionization:
= M/ 0M
At 0.001 M:
= M/ 0M 28/232.328
= 0.1205

At 0.01 M:
= M/ 0M 9.6/232.328
= 0.04132

At 0.1M:
= M/ 0M 3.3/232.328
= 0.01420

MM- 016
Using conductance measurements the degrees of dissociation for picric acid in
methanol were measured at 25oC in different concentrations. The results are as follows,
c (M)

0.001563
0.003125
0.00625
0.3131
0.2408
0.1820
Calculate the thermodynamic dissociation constant.

0.0125
0.1379

Solution:
Ka= 2c/ (1-) 1/= 1+ c/Ka which is a linear equation y=mx +b. If y is 1/ and x is c, then
the slope would be m= 1/Ka
A plot of 1/ vs. c was constructed.
c
0.001563
0.003125
0.00625
0.0125

c
1/

0.000489
0.3131 3.193868
0.000753
0.2408 4.152824
0.001138
0.182 5.494505
0.001724
0.1379 7.251632

1/ vs. c (Picric Acid)

y = 3,279.54713x + 1.65911
R = 0.99782

7
6

1/

5
4
3
2
1
0
0

0.0005

0.001
c

0.0015

0.002

The plot generates the equation of the line y = 3,279.54713x + 1.65911. The slope m= 1/Ka
would become Ka= 1/m.
Ka=1/m =1/3,279.54713
Ka= 3.049 x 10-4
Ka= 3.049 x 10-4

MM-030
The conductivity, at 18oC, of a saturated silver iodate solution is 1.9 x 10-3 S m-1
more than the water used to prepare the solution. The sum of the ionic limiting molar
conductivity of Ag+ and IO3- is found from measurements on more soluble salts to be 0.00873 S
m2 mol-1. (a) Calculate its solubility product at 18oC. (b) What value of the solubility is obtained if
it is assumed that no species other than Ag+ and IO3- is present in the solution?
Solution:
M= /c C= / M
C= 1.9 x 10-3 S m-1/ 0.00873 S m2 mol-1
C= 0.2176 mol m-3
Ksp= [Ag+][IO3-] =(0.2176 mol m-3)2
(a)
Ksp= 0.04734 mol2 mol-6
(b) solubility= 0.2176 mol m-3
solubility= 0.2176 mol m-3

MM-060
The moving boundary method was applied to a 0.02000 mol/dm3 aqueous NaCl
o
solution at 25 C using CdCl2 as the following solution. For a current held constant at 1.600mA, it
was found that the boundary moved 10.00 cm in 3453s in a tube of average cross-sectional
area 0.1115 cm2. The conductivity of this NaCl solution at 25oC is 0.002313 S cm-1. Calculate
uNa+ and tNa+ in this solution.
Solution:
= z+F += / zF
= 0.002313 S cm-1/(1x 9.648x104 C/mol)
Na+ = 2.3974 x 10-8

t= zcVF/It
V= 2r2l 2(0.1115)10 V= 2.23 cm3
C= 0.0200 mol/ dm3 = 2x10-5 mol /cm3
t= [(1)( 2x10-5 mol /cm3)( 2.23 cm3)( 9.648x104 C/mol)]/ (1.6x 10-3 A)(3453s)
tNa+= 0.77885