KOTEBE UNIVERSITY OF EDUCATION

DEPARTMENT OF CHEMISTRY

Chemical kinetics and electrochemistry

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Course content

1. Electrolytic solution

2. Electrochemical Cells

3. Interfacial Electrochemistry

4. Kinetic Theory of Gases

5. Chemical kinetics

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 Electrolyte Solutions
Introduction
•Electrical conductivity is the capacity of a substance to
transmit electricity.
The materials are called electrical conductors.
Electrical conductivity can be classified as:
•Metallic conductivity
•Electrolytic conductivity

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Example :

A 0.02 mol/dm3 solution of KCl has a conductivity of 0.00277 S cm-1

was found to have a resistance of 83 Ω. When 0.005 mol/dm3 of
potassium sulphate was substituted, the resistance was 326 Ω. What is
the (a) cell constant (l/A) and (b) conductivity (k) of potassium
sulphate and (c) molar conductivity of potassium sulphate (Λ).

l
(a)  k x R  0.0277 Ω 1cm 1 x 83 Ω  0.23 cm 1
A
1 l 1
(b) κ K SO   x 0.23 cm 1  7.05 x 10 4 Ω 1cm 1
2 4
R A 326 Ω
7.05 x 104 Ω 1cm 1 7.05 x 10 4 Ω 1cm 1dm 3 7.05 x 10 4 Ω 1cm 1 x 1000cm3
(c) λ  3
 
K 2SO4 0.005 mol dm 0.005 mol 0.005 mol
λ  141 S cm 2 mol1
K 2SO4

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Transport numbers
The transport number, t± is defined as the fraction of total current
carried by the ions of a specified type. For a solution of two kinds of
ion, the transport numbers of the cations (t+) and anions (t−) are

where I± is the current carried by the cation (I+) or anion (I−) and
I is the total current through the solution. Because the total
current is the sum of the cation and anion currents, it follows that
t+ + t− = 1

The limiting transport number, t±°, is defined in the same way but
for the limit of zero concentration of the electrolyte solution.
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For a strong electrolyte, the limiting molar conductivity at infinite dilution:

where ν+ and ν− are the numbers of cations and anions per formula
unit of electrolyte (for example, ν+ = ν− = 1 for HCl, NaCl, and CuSO4,
but ν+ = 1, ν− = 2 for MgCl2).

Since

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 Therefore,

However, because z+ν+ = z−ν− for any electrolyte

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Solved problems
1. The mobility of an acetate ion in aqueous solution at
25°C is 4.24 x 10-8 m2 s-1 V-1. Calculate the molar ionic
conductivity.

2. The mobility of a Li+ ion in aqueous solution is 4.01 x 10 -8

m2 s-1 V-1 at 25°C. The potential difference between two
electrodes placed in the solution is 12.0 V. If the electrodes
are 1.00 cm apart, what is the drift speed of the ion?

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3. What fraction of the total current is
carried by Cl − when current flows
through an aqueous solution of NaCl
at 25°C?

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4. The
limiting molar conductivities of NaI, NaCH3CO2, and
Mg(CH3CO2)2 are 12.69 mS m2 mol-1, 9.10 mS m2 mol-, and 18.78
mS m2 mol-, respectively (all at 25°C). What is the limiting molar
conductivity of MgI2 at this temperature?

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5. At 25°C the molar ionic conductivities of 𝐹−, 𝐶𝑙−, and Br− are 5.54 mS m2 mol−1, 7.635 mS
2 −1 2 −1
m mol , and 7.81 mS m mol , respectively. What are their mobilities?

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Techiniques used to determine transport number
1. Hittorf method

-based on concentration changes in the neighbourhoods of the

electrodes caused by the passage of current through the electrolytes.
If an electric current is passed
through a solution of an electrolyte,
the anions and cations move with
characteristic speeds toward the
anode and cathode.

These speeds vary with

magnitude of the:
• applied voltage,
• temperature and
• nature of individual
ions( charge and size) 17
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The velocity of H+ is three times greater than that of Cl-, the H+
ions will migrate from anode to cathode during a definite time over
a distance that is three times greater than that covered by Cl- from
cathode to anode.

Mobility (U+) = 3U-

∆nanode = 6-3 = 3 and ∆ncathode= 6-5 = 1
==

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 𝐐
𝐍𝐮𝐛𝐞𝐫 𝐨𝐟 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐜𝐚𝐭𝐢𝐨𝐧𝐬 𝐝𝐢𝐬𝐜𝐡𝐚𝐫𝐠𝐞𝐝(𝐜𝐚𝐭𝐡𝐨𝐝𝐞)=
𝐙+𝐅
𝐐
𝐍𝐮𝐛𝐞𝐫 𝐨𝐟 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐚𝐧𝐢𝐨𝐧𝐬𝐝𝐢𝐬𝐜𝐡𝐚𝐫𝐠𝐞𝐝 (𝐚𝐧𝐨𝐝𝐞)=
𝐙 −𝐅
𝐐 𝐐
𝐍𝐞𝐭 𝐥𝐨𝐬𝐬𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐞(𝐜𝐚𝐭𝐢𝐨𝐧𝐬)𝐟𝐫𝐨𝐦 𝐜𝐚𝐭𝐡𝐨𝐝𝐞=△ 𝒏𝒄= − 𝐭+
𝐙+𝐅 𝐙+𝐅

Therefore, and
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 MOVING BOUNDARY
Is a techinique for the determination of transport number in
which the motion of a boundary between two ionic solutions
having a common ion is observed as a current flows.
MX (leading solution) is the salt of interest
NX (indicator solution) is selected to give a
denser solution

where, Z- the charge number of ‘M’ ions

C is concentration in molarity

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EXC
During the electrolysis of a solution of potassium chloride between platinum electrodes,
0.0137 g of chloride was lost from the anodic compartment and 0.0857 g of silver was
deposited in a silver coulometer connected in series with the cell. Find the transport
number of K+and Cl–ions. Answer.0.4854; 0.5146
0
In moving boundary experiment with 0.100 N KCl using 0.065 N LiCl as indicator solution,
a constant current of 0.005893 amp was passed for 2130 seconds. The boundary was
observed tomove through 5.6 cm in a tube of 0.1142 sq cm cross-section. Calculate the
transport number of K+and Cl–ions.Answer.0.492; 0.508

A solution of silver nitrate containing 0.51 gm of the salt in 60.40 gm of the solution was
electrolysed under similar electrodes. After electrolysis 64 gm of the anode solution was
found to contain 0.56gm of silver nitrate. A current of 0.04 amp was passed for 2950
seconds. Calculate the transferencenumber of nitrate ion.Answer. 0.520(

A solution of HCl was electrolysed in a cell between two platinum electrodes. The cathode
compartmentcontained 0.354 g of chloride ions before electrolysis and 0.32 g after
electrolysis. A silver coulometer inseries had a deposit of 0.532 g of silver after passing the
same amount of current. Calculate the transportnumber of H+and Cl–
ions.Answer.0.84 ;0.160
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 ACTIVITY OF ELECTROLYTES
Interactions between ions are so strong that the approximation of
replacing activities by molalities is valid only in very dilute
solutions (less than 10−3 mol kg−1 in total ion concentration)

Activities in terms of molalities

In chemistry, compositions are often expressed as molalities,
b, in place of mole fractions. It therefore proves convenient to
write

For a compound MpXq that dissolves to give a solution

of p cations and q anions from each formula unit.

The mean activity coefficient (𝜸±)

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 DEBYE–HUCKEL THEORY
Electrolytes containing ions with multiple charges have greater
effects on the activity coefficients of ions than electrolytes
containing only singly charged ions.
To express electrolyte concentrations in a way that takes this
into account, G. N. Lewis introduced the ionic strength , defined
by

•Coulomb interaction is the main reason for

departing from ideality
•Oppositely charged ions attract each other and
will form shells (ionic atmosphere) screening
each other charge.
•The energy of the screened ion is lowered
as a result of interaction with its atmosphere 25
The Debye–Hückel limiting law
 Coulombic interaction b/n ions is responsible for departures from ideality in ionic solns.
 Basis of Debye–Hückel theory, devised by Peter Debye & Erich Hückel in 1923.
 At very low conc. activity coefficient can be calculated from Debye–Hückel limiting law

 A = 0.509 for an aqueous soln. at 25 °C, I is dimensionless ionic strength of solution, zi is

charge no. of an ion i (+ve for cations & -ve for anions) & bi is its molality.

 E.g. to get mean activity coefficient of 5.0 mmol kg−1 KCl(aq) at 25 °C:
• Calculate I by writing
• Then which is equal to 5.0 x 10 -3 6

Expt. Value is 0.927

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An experimental test of Debye–Huckel limiting law. Although there are marked deviations for
moderate ionic strengths, limiting slopes as I → 0 are in good agreement with theory,
so law can be used for extrapolating data to very low molalities.

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 When ionic strength of solution is too high for limiting law to be valid, the activity
coefficient may be estimated from extended Debye–Hückel law (sometimes called
Truesdell–Jones equation):

where B is a dimensionless constant

 A more flexible extension is Davies equation proposed by C.W. Davies in 1938:

where C is another dimensionless constant

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The Davies equation gives agreement with experiment over a wider range of molalities
than the limiting law (as shown hereElfeoctrrochaem1sitr,y1_C-haeptleer 4c_Totprioc 5lFyte), but it fails at higher
mola11lities.

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Examples
Calculate the ionic strength of a solution that is
0.040 mol kg-1 in K3[Fe(CN)6](aq), 0.030 mol kg-1
in KCl(aq), and 0.050 mol kg-1 in NaBr(aq).

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Calculate the masses of (a) KNO3 and, separately,
(b) Ba(NO3)2to add to a 0.110 mol kg-1 solution of
KNO3(aq) containing 500 g of solvent to raise its ionic
strength to 1.00.

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Estimate the mean ionic activity coefficient and activity of a
solution that is 0.020 mol kg-1 NaCl(aq) and 0.035 mol kg-1
Ca(NO3)2(aq).

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