Expt.

No: 9
THERMOCHEMISTRY - HEAT OF SOLUTION OF
POTASSIUM NITRATE IN WATER
Date:

AIM
To determine the ΔG, ΔH and ΔS of the potassium nitrate (KNO3) dissolving reaction by measuring
the equilibrium constant (Ksp) at different temperatures and using Van’t Hoff’s equation.

PRINCIPLE
In a saturated potassium nitrate (KNO3) solution in water, a dynamic equilibrium will be
established as, KNO3(s) ⇌ K+(aq) + NO− 3 (aq). The equilibrium constant Ksp (also called solubility
product constant) of this reversible reaction can be defined as, Ksp = [K+] [NO− +
3 ]. The [K ] is molar
concentration of K+ (mol/L) and [NO− −
3 ] is molar concentration of NO3 (mol/L).

The important thermodynamic parameters ΔG (free energy change), ΔH (enthalpy change) and
ΔS (entropy change) are related as, ΔG = ΔH – TΔS. The equation ∆𝐺 = −𝑅𝑇 ln𝐾𝑠𝑝 can be used to
obtain the Van’t Hoff’s equation.
∆𝐻 ∆𝑆
ln 𝐾𝑠𝑝 = − +
𝑅𝑇 𝑅
Determining the equilibrium constant(𝐾𝑠𝑝 ) at different temperatures and plotting ln 𝐾𝑠𝑝 data
versus 1/T data yields a straight line with a slope of –ΔH/R and a intercept of ΔS/R.
So, ΔH and ΔS can be calculated based on the linear equation. Then using ∆𝐺 = ∆𝐻 − 𝑇∆𝑆
relation, the ∆𝐺 for a particular temperature can also be calculated.

MATERIALS REQUIRED
Potassium nitrate salt (KNO3), 110C thermometer, deionized water, Boiling test tube,
500 mL beaker, 100 mL beaker, glass rod, 10 mL pipette, 2 mL pipette.
Molecular mass of KNO3 is 101.10 g/mol.

PROCEDURE
o About 10g of KNO3 salt is accurately weighed in a clean and dry boiling test tube (≈ 50 mL).
Exactly 10 mL of deionized water is added and heated (about 65C) in a water bath (or hot water
≈ 80𝐶 in a 500 mL beaker) to dissolve the salt completely for a clear solution.
o The solution is allowed to cool with smooth mixing and the temperature (T1) at which fine crystals
start to appear in solution is noted.
o Then, exactly 2 mL of water is added, mixed well and warmed to get clear solution. Allowed to
cool with gentle mixing to find the temperature (T2) at which the fine crystals start to appear. This
process is repeated four more times to get T3, T4, T5 and T6. The mass of KNO3, temperature and
volume data are tabulated.
o The mass of KNO3 taken remains constant whereas the volume varies from 10, 12, 14, 16, 18 and
20 mL with respective saturation temperatures varying from T1, T2, T3, T4, T5 and T6.
o The equal molar concentrations of [K+] and [NO−
3 ] are calculated as:
mass of KNO3 1000
[K+] = [NO3− ] =  mol/L
101.1 solution volume
o Then the equilibrium constant is calculated as, Ksp = [K+] [NO−
3 ].
OBSERVATIONS AND CALCULATIONS
Mass of KNO3 taken = ______ g
Solution Saturation
Molarity, M
Volume V Temperature, T 𝐾𝑠𝑝 1/T ln 𝐾𝑠𝑝
mol/L
(mL) (K)
10 273+…..
12 273+…..
14 273+…..
16 273+…..
18 273+…..
20 273+…..

Model Calculation and Graph

RESULT

The thermodynamic parameters for dissolution of KNO3 in water are:

ΔH = − slope  R = − …..………  8.314 = …………… kJ / mol
ΔS = intercept  R = ……………  8.314 = …………… kJ / mol
∆𝐺 = ∆𝐻 − 𝑇∆𝑆 = …..………  ………… = …………… kJ / mol