Activity of ions

To be precise in our equilibrium calculations instead of using concentrations we should

use ions activities. In fact whenever you put pH electrode into solution you are
measuring not [H+] but activity of H+ ions.

The difference between activity and other measures of composition arises because molecules in non-ideal
gases or solutions interact with each other, either to attract or to repel each other. The activity of an ion is
particularly influenced by its surroundings.

Activity is essentially the effective concentration.

Activity is related to concentration by the equation below:

𝑎 = 𝛾 𝑏 𝑏𝜃

Where 𝛾 is the activity coefficient; 𝛾 depends on the composition, molality and

temperature of the solution. b is the molality and 𝑏𝜃 is the standard molality (1
mol/kg). The division by 𝑏𝜃 is necessary to ensure that both the activity and the
activity coefficient are dimensionless.

Once we know the activity of a specie say j, its chemical potential is given by:
𝜇 = 𝜇𝜃 + 𝑅𝑇ln𝑎

Electrochemistry 1
The equation above helps us to derive the thermodynamic properties (such as
equilibrium constant) of solutions involving ions just in the same way for ideal
solution because we have replaced concentration by activity
Mean activity coefficient
If the chemical potential of a univalent cation 𝑀+ is denoted by 𝜇+ and that of a
univalent anion 𝑋 − is denoted by 𝜇− , the total Gibbs energy in the electrically
neutral solution is the sum of its partial molar quantities. For an ideal solution, this
is written as
𝑖𝑑𝑒𝑎𝑙 𝑖𝑑𝑒𝑎𝑙 𝑖𝑑𝑒𝑎𝑙
𝐺𝑚 = 𝜇+ + 𝜇−
However for a real solution of the same molality,

𝑮𝒎 = 𝝁+ + 𝝁− = 𝝁𝒊𝒅𝒆𝒂𝒍
+ + 𝝁𝒊𝒅𝒆𝒂𝒍
− + 𝑹𝑻𝐥𝐧𝜸+ + 𝑹𝑻𝐥𝐧𝜸−
= 𝑮𝒊𝒅𝒆𝒂𝒍
𝒎 + 𝑹𝑻𝐥𝐧𝜸+ 𝜸−

As we can see, all the deviations from ideality are contained in the last term

Electrochemistry 2
For a salt MX, M+ is the cation and 𝛾+ its activity. and 𝑋 − is the anion and 𝛾− its
activity.
Since cations and anions always occur together in an ionic solution, it is difficult to
assign the contribution of either the cation or the anion to the deviation from
ideality. The best we can do experimentally is to assign responsibility for the non
ideality equally to both kinds of ion. Therefore we introduce the mean activity
coefficient as the geometric mean of the individual coefficient.

𝟏
𝜸± = 𝜸+ 𝜸− 𝟐

For a salt 𝑀𝑝 𝑋𝑞 such as Mg3(PO4)2, where p = 3 and q = 2, the mean activity

coefficient is related to the activity coefficient of the individual ions as follows

𝟏
𝒑 𝒔
𝜸± = 𝜸+ 𝜸𝒒− 𝒔=𝒑+𝒒

Mean activity coefficient apportions deviation from ideality equally to the

cations and anions in an ionic solution.

Electrochemistry 3
 The Debye–Hückel theory
Activities are not a theoretical construct - they can be measured for every solution. In
fact whenever you put pH electrode into solution you are measuring not [H+] but
activity of H+ ions. Most popular method used to calculate ions activities is the one
proposed by Debye and Hückel in 1923.

The ionic atmosphere:

The long range and strength of the Columbic

interaction between ions means that it is
likely to be primarily responsible for
departure from ideality.
As a result of attraction, anions are likely to
be found around cations in solution and vice
versa.
The time average spherical haze, in which
counter ions outnumber ions of the same
charge as the central ion is called its ionic
atmosphere.

Electrochemistry 4
The energy, and therefore the chemical potential, of any given central ion is lowered as
a result of its electrostatic interaction with its ionic atmosphere. This lowering of
energy appears as the difference between the molar Gibbs energy Gm and the ideal
𝑖𝑑𝑒𝑎𝑙
value 𝐺𝑚 of the solute and hence can be identified again with 𝑅𝑇ln𝛾± .

This ionic atmosphere concept is one of the reasons why chemist use dilute solution to
achieve precipitation of ions from electrolyte solution.

This model leads to the result that at very low concentration, the activity coefficient
can be calculated from the Debye – Huckel limiting law:

log𝛾± = −𝐴 |𝑧+ 𝑧− |𝐼 1 2

𝐴 is a constant which works out to be 0.509 for water at 25 ℃. The 𝑧 are the charge
numbers of the ions (𝑧+ = +1 for Na+ and 𝑧− = -2 for SO42-.

The quantity I is the ionic strength of the solution. It is defined as

1 2
𝐼 = 𝑧+ 𝑏+ + 𝑧−2 𝑏−
2

Electrochemistry 5
 For solutions more more concentrated than about 1 mM, we use the
extended Debye – Huckel law:

𝐴|𝑧+ 𝑧− |𝐼 1 2
log𝛾± = − + 𝐶𝐼
1 + 𝐵𝐼 1 2

The Debye-Huckel theory ascribes deviation from ideality to the Columbic

interaction of an ion with the ionic atmoshpere that assembles around it.

Electrochemistry 6
 The migration of ions

Ions are mobile in solution, and the study of their motion down a potential
gradient gives an indication of their size, the effect of solvation, and details of
the type of motion they undergo. The migration of ions in solution is studied by
measuring the electrical resistance of a solution of known concentration. The
resistance, R (in ohms, Ω), of the solution is related to the current, I (in
amperes, A), that flows when a potential difference, V(in volts, V), is applied
between the two electrodes, by Ohm’s law: V=IR

Resistivity
𝑙
𝑅 = 𝜌 𝐴 . 𝜌 is a constant of proportionality called resistivity with unit 𝛺𝑚

1
= 𝜅 = 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑤𝑖𝑡ℎ 𝑢𝑛𝑖𝑡 𝛺−1  𝑚−1 .  
𝜌
𝛺 −1  𝑖𝑠 𝑎𝑙𝑠𝑜 𝑐𝑎𝑙𝑙𝑒𝑑 𝑠𝑖𝑒𝑚𝑒𝑛𝑠 𝑤𝑖𝑡ℎ 𝑠𝑦𝑚𝑏𝑜𝑙 𝑆

Electrochemistry 7
molar conductivity, Λm

𝜅
𝛬𝑚 =
𝑐
With molar concentration in moles per cubic decimetre, molar conductivity is expressed
in siemens per metre per (moles per cubic decimetre), or S m−1 (mol dm−3)−1. These
awkward units are useful in practical applications but can be simplified to siemens
metre squared per mole (S m2 mol−1). Specifically, the relation between units is 1 S m−1
(mol dm−3)−1 = 1 mS m2 mol−1, where 1 mS = 10−3 S.

Molar conductivity of strong electrolytes

The molar conductivity of a strong varies with molar concentration in

accord with the empirical law discovered by Friedrich Kohlrausch in 1876:
𝛬𝑚 = 𝛬∘𝑚 − 𝐾𝑐 1 2

Electrochemistry 8
Example 9.1
Determining the acidity constant from the conductivity of a weak acid
The molar conductivity of 0.010 M CH3COOH(aq) is 1.65 mS m2 mol−1. What is
the acidity constant of the acid?

Strategy Because acetic acid is weak, it is only partly deprotonated in aqueous

solution. Only the fraction of acid molecules present as ions contributes to the
conduction, so we need to express Λm in terms of the fraction deprotonated. To
do so, we set up an equilibrium table, find the ions, and relate molar
concentration of H3O+ and those concentrations to the observed molar
conductivity.

Thermodynamics 9
9.1 Calculate the ionic strength of a solution that is 0.15 mol kg−l in KCl(aq)
and 0.30 mol kg−1 in CuSO4(aq).

9.2 Calculate the masses of (a) Ca(NO3)2 and, separately, (b) NaCl to add to a
0.150 mol kg−1 solution of KNO3(aq) containing 500 g of solvent to raise its
ionic strength to 0.250.

9.3 Express the mean activity coefficient of the ions in a solution of MgF2 in
terms of the activity coefficients of the individual ions.

9.4 Estimate the mean ionic activity coefficient and activity of a solution that
is 0.015 mol kg−1 MgF2(aq) and 0.025 mol kg−1 NaCl(aq).

9.5 The mean activity coefficients of HBr in three dilute aqueous solutions at
25°C are 0.930 (at 5.0 mmol kg−1), 0.907 (at 10.0 mmol kg−1), and 0.879 (at
20.0 mmol kg−1). Estimate the value of B in the extended Debye–Hückel law.

Thermodynamics 10
9.1 Calculate the ionic strength of a solution that is 0.15 mol kg−l in KCl(aq) and 0.30 mol kg−1 in CuSO4(aq).

Answer:1.35

9.2 Calculate the masses of (a) Ca(NO3)2 and, separately, (b) NaCl to add to a 0.150 mol kg−1 solution of KNO3(aq) containing 500 g of
solvent to raise its ionic strength to 0.250.

Answer:(a) 2.73 g
(b) 2.92 g

9.3 Express the mean activity coefficient of the ions in a solution of MgF2 in terms of the activity coefficients of the individual ions.

Answer:

9.4 Estimate the mean ionic activity coefficient and activity of a solution that is 0.015 mol kg−1 MgF2(aq) and 0.025 mol kg−1 NaCl(aq).

9.5 The mean activity coefficients of HBr in three dilute aqueous solutions at 25°C are 0.930 (at 5.0 mmol kg−1), 0.907 (at 10.0 mmol
kg−1), and 0.879 (at 20.0 mmol kg−1). Estimate the value of B in the extended Debye–Hückel law.

Answer:B = 2.01

Thermodynamics 11
 c/M 0.0005 0.001 0.005 0.010 0.020 0.050
(c/M)1/2 0.0224 0.0316 0.0707 0.1 0.141 0.224
R/Ω 3314 1669 342.1 174.1 89.08 37.14
m (mS m2 mol 1 ) 12.45 12.36 12.06 11.85 11.58 11.11

The plot is linear. Hence Kohlraush’s law is obeyed.

9.6 The limiting molar conductivities of KCl, KNO3, and AgNO3 are 14.99 mS m2 mol−1, 14.50 mS m2 mol−1
and 13.34 mS m2 mol−1, respectively (all at 25°C). What is the limiting molar conductivity of AgCl at this
temperature?

Answer:13.83 mS m2 mol−1

9.7 The mobility of a chloride ion in aqueous solution at 25°C is 7.91 × 10−8 m2 s−1 V−1. Calculate its molar
ionic conductivity.

Answer:7.63 mS m2 mol−1

9.8 The mobility of a Rb+ ion in aqueous solution is 7.92 × 10−8 m2 s−1 V−1 at 25°C. The potential difference
between two electrodes placed in the solution is 35.0 V. If the electrodes are 8.00 mm apart, what is the drift
speed of the Rb+ ion?

9.9 The resistances of a series of aqueous NaCl solutions, formed by successive dilution of a sample, were
measured in a cell with cell constant (the constant C in the relation k = C/R) equal to 0.2063 cm−1. The
following values were found:

(a) Verify that the molar conductivity follows the Kohlrausch law and find the limiting molar conductivity. (b)
Determine the coefficient K. (c) Use the value of K (which should depend only on the nature, not the identity
of the ions) and the information that λ(Na+) = 5.01 mS m2 mol−1 and λ(|−) = 7.68 mS m2 mol−1 to predict (i)
the molar conductivity, (ii) the conductivity, (iii) the resistance it would show in the cell, of 0.010 mol dm−3
NaI(aq) at 25°C.

Thermodynamics 13
An electrochemical cell consists of two electronic conductors (metal or graphite, for
instance) dipping into an electrolyte (an ionic conductor), which may be a solution,
a liquid, or a solid
A galvanic cell (also called a voltaic cell) is an electrochemical cell that produces
electricity as a result of the spontaneous reaction occurring inside it. An electrolytic
cell is an electrochemical cell in which a nonspontaneous reaction is driven by an
external source of direct current.

Electrochemistry 14
Define terms like electrode, electrolyte, redox reaction, oxidation, reduction

A half-reaction is the part of an overall reaction that represents, separately, either

an oxidation or a reduction. Two half-reactions, one oxidation and one reduction,
are necessary to completely describe a redox reaction

Any redox reaction may be expressed as the difference of two reduction

half-reactions. Two examples are

The oxidized and reduced species in a half-reaction form a redox couple,

denoted Ox/Red
Couple: Ox/Red Half-reaction: Ox + v e− → Red
𝐹𝑒 3+ + 𝑒 − → 𝐹𝑒 2+

Electrochemistry 15
 A half reaction is a reduction or an oxidation reaction. For example, the
following are half reactions.
2 H+ + 2 e-  H2
MnO4- + 5 e- + 8 H+  Mn2+ + 4H2O
Zn  Zn2+ + 2 e-
Cu  Cu2+ + 2 e-

A half reaction does not occur by itself, at least two such reactions must be coupled so
that the electron released by one reactant is accepted by another in order to complete
the reaction. Thus, oxidation and reduction reactions must take place simultaneously in
a system, and this type of reactions is called oxidation reduction reaction or simply
redox reaction. For example

Electrochemistry 16
Zinc metal and Zn2+ ion form a redox couple, Zn2+ being the oxidant, and Zn the reductant. The
same notation was used to designate a redox couple earlier. Similarly, when a stick of copper
(Cu) is inserted in a copper salt solution, there is also a tendency for Cu to loose electron
according to the reaction, Cu = Cu2+ + 2 e-. This is another half cell or redox couple: Cu | Cu2+.

However, the tendency for Zn to loose electron is stronger than that for copper. When the two
cells are connected by a salt bridge and an electric conductor as shown to form a closed circuit
for electrons and ions to flow, copper ions (Cu2+) actually gains electron to become copper
metal. The reaction and the redox couple are respectively represented below,
Cu2+ + 2 e- = Cu, Cu2+ | Cu.
This arrangement is called a galvanic cell or battery as shown here. In a text form, this battery is
represented by, Zn | Zn2+ || Cu2+ | Cu,

Electrochemistry 17
In an electrochemical cell, the anode is where oxidation takes place and the cathode is
where reduction takes place. However, the polarity is different when galvanic and
electrolytic cells are considered

Galvanic cell Electrolytic cell

Electrochemistry 18
In a gas electrode, a gas is in equilibrium with a solution of its ions in the
presence of an inert metal

This electrode is denoted Pt(s)|H2(g)|H+(aq). The vertical

lines denote junctions between phases. In this electrode,
the junctions are between the platinum and the gas and
between the gas and the liquid containing its ions

Electrochemistry 19
A metal–insoluble-salt electrode consists of a metal M covered by a porous layer of
insoluble salt MX, the whole being immersed in a solution containing X− ions .The
electrode is denoted M|MX |X−, where the vertical line denotes a boundary across
which electron transfer takes place. An example is the silver–silver-chloride electrode,
Ag(s)|AgCl(s)|Cl−(aq), for which the reduction half-reaction is

Electrochemistry 20
The term redox electrode is normally reserved for an electrode in which the couple
consists of the same element in two nonzero oxidation states (Fig. 9.11). An example
is an electrode in which the couple is Fe3+/ Fe2+. In general, the equilibrium is
Figure 9.11 The schematic structure of a redox electrode. The platinum metal acts as
a source or sink for electrons required for the interconversion of (in this case) Fe2+
and Fe3+ ions in the surrounding solution.

Electrochemistry 21
First law: The mass of substance deposited is directly proportional to the quantity of
current passed
𝒘 𝜶 𝑸   𝒐𝒓  𝒘 𝜶 𝑰𝒕

Where Q is the quantity of electricity passed and has a unit C (coulombs).

The equation can be rewritten as

𝒘  = 𝒛𝑸 .
Where z is a constant of proportionality called electrochemical equivalence which can
be defined as the mass of substance deposited, when one Faraday of current is passed
for one second. (or when one coulomb of current is passed).

The equation for faradays first law can thus be written as

𝑨𝑸
𝒘  =
𝒏𝑭
𝑤ℎ𝑒𝑟𝑒 𝐴 𝑖𝑠 𝑡ℎ𝑒 𝑎𝑡𝑜𝑚𝑖𝑐 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑏𝑠tan𝑐𝑒,  
𝑄 𝑖𝑠 𝑡ℎ𝑒 𝑞𝑢𝑎𝑛𝑡𝑖𝑡𝑦 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑖𝑡𝑦 𝑝𝑎𝑠𝑠𝑒𝑑,  
𝑛 𝑖𝑠 𝑡ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑜𝑛𝑠 𝑎𝑛𝑑 𝐹 𝑖𝑠 𝐹𝑎𝑟𝑎𝑑𝑎𝑦′𝑠  𝑐𝑜𝑛𝑠tan𝑡

Electrochemistry 22
 Faraday constant (named after Michael Faraday) is the magnitude of electric
charge per mole of electrons.
1𝐹 = 96485 𝐶𝑚𝑜𝑙 −1
It can also be related to the equation 𝐹 = 𝑒𝑁𝑎
Where 𝑁𝑎 is Avogadro constant and 𝑒 the magnitude of the charge of an electron

Q 6.1 let's calculate the number of grams of sodium metal that will form at the
cathode when a 10.0-amp current is passed through molten sodium chloride for a
period of 4.00 hours.
Q 6.2 Calculate the volume of H2 gas at 25oC and 1.00 atm that will collect at the
cathode when an aqueous solution of Na2SO4 is electrolyzed for 2.00 hours with a
10.0-amp current
Q6.3 If 0.025 A was passed through a solution until 1.200g of Au had been
deposited at the cathode, a) calculate the quantity of electricity passed through the
solution. B) calculate the time taken for the experiment. C) calculate the volume of
oxygen gas generated at the anode at stp
Q6.4 Determine the oxidation number of the chromium in an unknown salt if
electrolysis of a molten sample of this salt for 1.50 hours with a 10.0-amp current
deposits 9.71 grams of chromium metal at the cathode.
2 H2O(l) + 2 e- → H2(g) + 2 OH-(aq) Electrochemistry 23
Faraday’s 2nd law: When the same quantity of electricity is passed through different
electrolytes connected in series the weight of substances deposited at the electrodes is
directly proportional to their equivalent weight.
OR
When the same amount of charge is made to pass through any number of electrolytes,
the mass of the substance liberated or deposited at the electrodes are directly
proportional to their chemical equivalents

To deposit one mole of a substance we must pass an integral number of

Faraday's.
Example:
For one mole of sodium (at. wt 23) = 1F
For one mole of calcium (at. wt 40) = 2F
For one mole of Aluminium (at. wt 27) = 3F

Q6.5 In an electrolytic cells containing AgNO3, MgCl2, and Au(NO3)3 salts arranged in
series, after 2 hours, the mass of the cathode in the second cell increased by 59.05
g. Calculate a) the mass of silver deposited at the first cell. b) the moles of gold
deposited in the third cell. c) the amount of current passed through the electrolytic
cell. d) If this reaction took place at standard temperature and pressure, what
volume of chlorine gas will be liberated in the second cell.

Electrochemistry 24
The potential difference measured when a cell is balanced against an external
source of potential is called the cell potential and denoted Ecell

Maximum non expansion work is given by:

′
𝑤max = 𝛥𝐺 (6.1)
We can relate cell potential with Gibbs energy by the equation:
𝛥𝐺 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 (6.2)
When the reaction is spontaneous, 𝛥𝐺 < 0 𝑎𝑛𝑑 𝐸𝑐𝑒𝑙𝑙 > 0. At equilibrium,
𝛥𝐺 = 0 and 𝐸𝑐𝑒𝑙𝑙 = 0

Electrochemistry 25
A galvanic cell does electrical work as the reaction drives electrons through an
external circuit. The work done by a given transfer of electrons depends on the
potential difference between the two electrodes. This potential difference is
measured in volts (V, where 1 V = 1 J C−1).

′
𝑤max = 𝛥𝐺𝑟

Therefore, by measuring the potential difference and converting it to the electrical

work done by the reaction, we have a means of determining a thermodynamic
quantity, the reaction Gibbs energy

The potential difference measured when a cell is balanced against an external

source of potential is called the cell potential and denoted E. The relationship
between emf and Gibb’s energy is

−𝑛𝐹𝐸 = 𝛥𝐺𝑟

Electrochemistry 26