KYAMBOGO UNIVERSITY

FACULTY OF SCIENCE
DEPARTMENT OF CHEMISTRY
B.Sc. CHEMICAL ENGINEERING
PHYSICAL CHEMISTRY COURSE WORK
NAMES
REGISTRATION
NUMBERS
KASAJJA ISAAC 15/U/136/CHD/GV
AGABA COLLINS 15/U/131/CHD/GV
MURUNGI CHARITY 15/U/139/CHD/GV
OGENRWOT MOSES 15/U/5231/CHD/PD
NABATEREGGA JOAN 15/U/5215/CHD/PD
NYAGO DEOGRATIUS 15/U/5328/CHE/PE
TUMWESIGE GEOFREY 15/U/13123/CHD/GV
KOONA JIMMY 15/U/5190/CHD/PD
OGOMARACH RACHEAL 15/U/4403/CHE/PE
KATOOKO BRIGET 15/U/5178/CHD/PD
GOLJOK KAU 15/X/5171/CHD/PD
Qn; what is the significance and equations for calculating the following;

a) Internal energy.
b) Enthalpy.
c) Entropy.
d) Gibb’s free energy.

Answers
From the first law of thermodynamics energy can neither be created nor destroyed.

Chemically that usually means energy is converted to work, energy in form of heat moves from one
place to another, or energy is stored up in the constituent chemicals.

Mathematically, we can look at the change in energy of the system as being a function of both heat and
work which is internal energy.

INTERNAL ENERGY

Internal energy in a system arises from relative positions and interactions of its molecules.

∆ U =q+ w
∆ U is change∈internal energy of the system ;
q is energy flowing into ¿
w is the work done by the system¿
The total internal energy in the system includes potential and kinetic energy. Internal energy includes energy on the microscopic scale and it’s
the sum of all microscopic energy such as;

(i) Translational kinetic energy

(ii) Vibrational and rotational kinetic energy
(iii) Potential energy from inter-molecular forces.
∆U is directly proportional to temperature of the system. Internal energy of an ideal gas system can be measured directly because
intermolecular forces of attraction are not considered.
3 J
∆ U = RT where R−gas constant ∈ ∧T −temperature ∈K
2 molK
The internal energies of more complex systems can’t be measured directly but can be monitored by watching the temperature.

ENTHALPY
Enthalpy is a state function just like internal energy. A state function is a variable that depends only on the present condition of the system.
These include temperature, pressure, and volume.

Enthalpy is a state function because it’s defined by internal energy, pressure and volume.

H=U + PV where Pis pressure ,V is volume ,U is internalenergy∧H is enthalpy

Enthalpy can be calculated directly by taking the final and initial states of the system.

∆ H =H ( final∨ products ) −H ( initial∨reactants )

We can also determine change in enthalpy for a reaction based on bond dissociation of energies. Breaking bonds requires energy while forming
bonds releases energy.

Hess’ law

The overall enthalpy change for a particular reaction is the same regardless of the route of reaction. For instance ∆ H ϑf ( C H 4 ) can be
obtained from the knowledge of standard enthalpy of a reaction of the following equations

C+ O 2 → CO2

2 H 2+O 2 → H 2 O
CH 4 +2 O 2 → CO2 +2 H 2 O

Relationship between ∆ H and T

T
∆ H ( T )=∆ H ( 298 K )+ ∫ ∆C °p dT
θ θ

298

Other useful enthalpies include; enthalpy of vaporization, fusion, sublimation, combustion, hydrogenation and hydration.

Enthalpy determines whether the reaction gives off heat or not

Example 1.

Calculate the change in enthalpy value of the reaction HCl+ N H 3 → NH 4 Cl ¿

Solution.

∆ H =∆ H ( products )−∆ H ( reactants )

∆ H =−314.4−(−92.30±80.29)
∆ H =+141.8 kJ /mol

Example 2

Calculate the change in enthalpy for the reaction; N 2 +3 H 2 → 2 NH 3 ¿.

Solution.

∆ H =∆ H products −∆ H reactants

To use bond dissociation energies, we must determine how many bonds are in the products and the reactants.

Compound Bonds broken Bonds formed

NH3 3N-H
H2 3 H-H
N2 1 N-N

∴ ∆ H=6 ( 391 )− [ (3∗436 ) +163 ]

∆ H =875 kJ /mol
Example 3

Calculate the change in the enthalpy for a combustion reaction given that∆ U =−100 KJ∧W =10 KJ

Solution

∆ H =∆ U +W
 ¿−100+10
¿−90 KJ
Example 4

Calculate the enthalpy of a reaction for N 2 (g) +3 H 2(g ) → 2 NH 3 ( g) at 450 K using the following for the heat capacities;

C p ( N 2) =3.5 R ,C p ( H 2 )=3.5 R ,C p (NH ¿¿ 3)=4 R ¿ . Its is known that

∆ H °f ( NH 3 ) , 298 K=−45.72 kJ /mol
Solution

∆ H ° ( 298 K )=( 2∗−45.72 ) −( 1∗0 )−( 3∗0 )=−91.44 kJ /mol

∆ C °p=2 C p ( NH 3 )−C p ( N 2 )−3 C p ( H 2 )

450
∆ H ° ( 450 K ) =∆ H ° ( 298 K )+ ∫ C°p dT =−91440−49.9 ( 450 )−298=−99.02 kJ /mol
298

ENTROPY

Entropy is the degree of the molecular disorder of a system. Take your room as an example. Left to itself, your room will increase in entropy if
no work (cleaning up) is done to contain the disorder. Alternatively, for a particular substance for example water we expect the entropy to
increase in the order of solid – liquid – gas by the molecular disorder argument. Work must be done to keep the entropy of the system low.
Entropy comes from the second law of thermodynamics, which states that all systems tend to reach a state of equilibrium. The significance of
entropy is that when a spontaneous change occurs in a system, it will always be found that if the total entropy change for everything involved is
calculated, a positive value will be obtained. Simply, all spontaneous changes in an isolated chemical system occur with an increase in entropy.

Entropy, like temperature, pressure, and enthalpy, is a state property normally represented by “S” and the change of S

∆ S=S ( final / products )−S (Initial/reactants)

Where:

∆ S=change∈ entropy
Sfinal and Sinitial are the final and initial entropies, respectively.

d Q rev
Change in entropy can also be calculated by; ∆ S system =
T
where Q isthe heat of the system∧T istemperature of the system.
Variation of entropy with temperature.

T
° ° ∆ C°p
∆ S ( T )=∆ S ( 298 K ) + ∫ dT
298 T
Entropy describes the molecular state of the system

Example
Calculate the standard entropy change for the reaction of N 2 +3 H 2 → 2 N H 3 at 450k using the data given CP(N2) = 28.67 + 0.00155T,
CP(H2) = 28.25 + 0.00218T, CP(NH3) = 26.19 + 0.03159T and the following standard entropy values at 298K,

S° ( N 2 ) =191.6 , S° ( H 2 ) =130.7 , S ° ( NH ¿ ¿3)=192.5 J /molK ¿

Solution

−198.7 J
∆ S° ( 298 K )= ( 2∗192.5 )− (1∗191.6 )− (3∗130.7 ) =
molK
∆ C P =2C P ( NH 3 )−C P ( N 2) −3 C P ( H 2 )=−61.04 +0.05509 T
450
° ° ∆ CP
∆ S ( 450 K )=∆ S ( 298 K ) + ∫ dT
298 T

¿−198.75−61.04 ∈ ( 450
298 )
+ 0.05509 ( 450−298 ) =−213.5 J / Kmol

Gibbs free energy

The free energy of a system, represented by letter “G”, is defined as the energy of a system that is free to do work at constant temperature and
pressure. Mathematically, it defined as:

G=H −TS
Where:

G is the energy

H is the enthalpy

T is the temperature

S is the entropy of the system

Gibbs free energy is also calculated the same way as you calculate enthalpy or entropy:

∆ G=G ( products )−G ( reactants )

Where:

∆ G is change∈free energy
Gibbs free energy determines whether the a chemical reaction is feasible or not

Calculate the standard Gibbs free energy change for the reaction for N 2 ( g )+ 3 H 2 ( g)→2 NH 3 ( g) at 298K and 450K given
−91.44 KJ −97.59 KJ −198.7 KJ
∆ H ° ( 298 K )= ∆ H ° ( 450 K )= ∆ S ° ( 298 K )= ∆ S° ( 450 K ) =−215.5 KJ /mol
mol mol mol

∆ G ° ( 298 K )=−91440−298 (−198.7 )=−32.23 KJ /mol

∆ G ° ( 450 K ) =−97590−450 (−215.5 )=−0.62 KJ /mol

Example

Given the following entropy values Al2O3(s) is 51.00 kJ/mol; Al(s) is 28.32 kJ/mol; H2O(g) is 188.7 kJ/mol; H2(g) is 130.6 kJ/mol, determine
∆ s for thereaction : A l 2 O 3 (s) +3 H 2(g ) → 2 A l (s) +3 H 2 O (g)
∆ s=∆ s ( pdts )−∆ s( rxts)

¿ [ ( 2∗28.32 ) + ( 3∗188.7 ) ]−¿

¿ 179.94 KJ /mol