• Midterm exam location

Odette Building, room 104

Feb. 3rd from 1 - 2:20 p.m.
March 10th from 1 - 2:20 p.m
 Solutions contain more than one types of
electrolytes
• The ionic strength of the solution equals the sum of the ionic
strength of each individual compound.

Example: Calculate the ionic strength of a solution that contains 0.050

mol kg-1 K3[Fe(CN)6](aq), 0.040 mol kg-1 NaCl(aq), and 0.03 mol kg-1
Ce(SO4)2 (aq).

Solution:
I (K3[Fe(CN)6]) = ½( 12*(0.05*3) + (-3)2*0.05)
= ½ (0.15 + 0.45) = 0.3;
I (NaCl) = ½(12*0.04 + (-1)2*0.04) = 0.04;
I (Ce(SO4)2) = ½(42*0.03 + (-2)2*(2*0.03)) =0.36;

So, I = I(K3(Fe(CN)6]) + I(NaCl) + I(Ce(SO4)2)

= 0.3 + 0.04 + 0.36 = 0.7
Calculating the mean activity coefficient

Example: Calculate the ionic strength and the mean activity coefficient
of 2.0m mol kg-1 Ca(NO3)2 at 25 oC.

Solution: In order to calculate the mean activity coefficient with the eq.
10.3, one needs to know the ionic strength of the solution. Thus, the
right approach is first to get I and then plug I into the equation 10.3.

I = ½(22*0.002 + (-1)2*(2*0.002)) = ½ *6*0.002 = 0.006;

From Debye-Huckel limiting equation,

log(γ±) = - |2*1|*A*(0.006)1/2;
= - 2*0.509*0.0775;
= -0.0789;

γ± = 0.834;
Experimental test of the Debye-Hückel
limiting law
 Accuracy of the Debye-Hückel limiting law

Example: The mean activity coefficient in a 0.100 mol kg-1 MnCl2(aq)

solution is 0.47 at 25oC. What is the percentage error in the value
predicted by the Debye-Huckel limiting law?

Solution: First, calculate the ionic strength

I = ½[22*0.1 + (-1)2*(2*0.1)] = 0.3

to calculate the mean activity coefficient.

log(γ) = -|2*(-1)| A* (0.3)1/2;
= - 2*0.509*0.5477
= - 0.5576
so γ = 0.277

Error = (0.47-0.277)/0.47 * 100%

= 41%
 Extended Debye-Hückel law

• A | z z | I 1 / 2
log(  )  
1  BI 1 / 2

B is an adjustable empirical
parameter. It is different for each
electrolyte.
 Calculating parameter B
Example : The mean activity coefficient of NaCl in a diluted aqueous solution at
25oC is 0.907 (at 10.0 mmol kg-1). Estimate the value of B in the extended
Debye-Huckel law.

Solution: First calculate the ionic strength

I = ½[12*0.01 + (-1)2*0.01] = 0.01

A | z z | I 1 / 2
From equation log(  )  
1  BI 1 / 2

log(0.907) = - (0.509|1*(-1)|*0.011/2)/(1+ B*0.011/2)

B = - 1.67
 Half-reactions and electrodes
Two types of electrochemical cells:

1. Galvanic cell: is an electrochemical cell which

produces electricity as a result of the spontaneous
reactions occurring inside it.

2. Electrolytic cell: is an electrochemical cell in which

a non-spontaneous reaction is driven by an external
source of current.
• Other important concepts include:

Oxidation: the removal of electrons from a species.

Reduction: the addition of electrons to a species.
Redox reaction: a reaction in which there is a transfer of electrons
from one species to another.
Reducing agent: an electron donor in a redox reaction.
Oxidizing agent: an electron acceptor in a redox reaction.

• Two type of electrodes:

Anode: the electrode at which oxidation occurs.
Cathode: the electrode at which reduction occurs
Typical Electrodes
 Electrochemical cells
• Liquid junction potential: due to the
difference in the concentrations of
electrolytes.

• The right-hand side electrochemical

cell is often expressed as follows:
Zn(s)|ZnSO4(aq)||CuSO4(aq)|Cu(s)

• The cathode reaction (copper ions

being reduced to copper metal) is
shown on the right. The double bar (||)
represents the salt bridge that separates
the two beakers, and the anode
reaction is shown on the left: zinc
metal is oxidized into zinc ions
In the above cell, we can trace the movement of charge.
– Electrons are produced at the anode as the zinc is oxidized
– The electrons flow though a wire, which we can use for electrical energy
– The electrons move to the cathode, where copper ions are reduced.
– The right side beaker builds up negative charge. Cl- ions flow from the salt bridge
into the zinc solution and K+ ions flow into the copper solution to keep charge
balanced.

To write the half reaction for the above cell,

Right-hand electrode: Cu2+(aq) + 2e- → Cu(s)
Left-hand electrode: Zn2+(aq) + 2e- → Zn(s)

The overall cell reaction can be obtained by subtracting

left-hand reaction from the right-hand reaction:
Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)
 Expressing a reaction in terms of
half-reactions
Example : Express the formation of H2O from H2 and O2 in
acidic solution as the difference of two reduction half-
reactions.
(in class discussion)
Redox couple: the reduced and oxidized species in a half-
reaction such as Cu2+/Cu, Zn2+/Zn….
Ox + v e- → Red

The quotient is defined as: Q = aRed/aOx

Example: Write the half-reaction and the reaction quotient

for a chlorine gas electrode.
(in class discussion)
Varieties of cells
 Notation of an electrochemical cell
• Phase boundaries are
denoted by a vertical
bar.
• A double vertical line,
||, denotes the
interface that the
junction potential has
been eliminated.
• Start from the anode.

A general format:
Solid | gas phase | aqueous phase || aqueous phase | gas phase | solid
 Cell Potential
• Cell potential: the potential difference between two electrodes of a
galvanic cell (measured in volts V).

• Maximum electrical work : we,max = ΔG

• Electromotive force, E,

• Relationship between E and ΔrG:

ΔrG = -νFE
where ν is the number of electrons that are exchanged during the
balanced redox reaction and F is the Faraday constant, F = eNA.

• At standard conditions, this equation can be written as

ΔrGθ = -νFEθ