Physical Chemistry II

(CHE26M1)
Lecture #2a:
st
1 Law of
Thermodynamics
Internal Energy, Heat and Work
1st Law of Thermodynamics:
• Law of energy conservation: Energy cannot be created or
destroyed. It is transferred from one form (or place) to
another. Introduces a relationship between Internal Energy
(U), Work (W) and Heat (q): ∆𝑼 = 𝒒 + 𝒘
∆U = q – w ∆U = q + w
• The increase (change) in the internal energy(U) of a system
is equal to the amount of heat (q) added to the system, Internal Energy: Energy of a system
plus the amount of work (w) done on the system. in a form of kinetic energy and
potential energy of molecules
Work (w): Energy related to a force
𝒅𝑼 = 𝒅𝒒 + 𝒅𝒘 acting over a distance and causes
motion against an opposing force.
න 𝒅𝑼 = න 𝒅𝒒 + න 𝒅𝒘 Heat (q): Transfer of energy as a
result of a temperature difference
between the system and
∆𝑼 = 𝑈𝑓𝑖𝑛𝑎𝑙 − 𝑈𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝒒 + 𝒘 surrounding (e.g heating and
cooling water)
(net work done on the system by the surrounding)
 State Functions: Path independent Non-state functions: Path dependent

State function, a property of a system that is determined by Non-State function such as q and w. This means that, although
specifying the system’s condition, or state (in terms of ∆T, ∆V, ∆U does not depend on how the change occurs, the specific
∆P, ∆n, ∆U). The value of a state function depends only on the amounts of heat and work produced depend on the way in
present state of the system, not on the path the system took to which the change occurs. Non-state function depends on the
reach that state. Always has a value. Because U is a state path the system took to reach that state
function, ∆U depends only on the initial and final states of the
system, not on how the change occurs. 𝟐
‫ = 𝒘𝒅 𝟏׬‬w (NB: ∆w and ∆q does not exist)
𝟐
‫ = 𝑼𝒅 𝟏׬‬U2-U1 = ∆U (state function) 𝟐
‫ = 𝒒𝒅 𝟏׬‬Q
∆P = Pfinal - Pinitial
∆V = Vfinal - Vinitial
‫ ׬‬dw = w1 + w2 + w3 … (We can add work and heat
∆T = Tfinal - Tinitial done on (by) a system)
∆U = Ufinal - Uinitial D ‫ ׬‬d𝒒 = q1 + q2 + q3 …
W3, q3
C
W2, q2

B
W1, q1
∆U of a Chemical System
• Internal Energy is all the energy contained
∆U < 0
in a system including both kinetic energy and potential energy. exothermic
• In a chemical reaction, the initial state of the system refers to the
reactants and the final state refers to the products:
• When hydrogen and oxygen form water at a given
Ui Uf
temperature, the system loses energy to the surroundings
• Because energy is lost from the system, the internal energy Final state
Initial state
of the products (final state) is less than that of the reactants
(initial state), and U for the process is negative (< 0)
∆U = Ufinal - Uinitial
Positive (+ve) ∆U  system gained energy from surrounding
Negative (-ve) ∆U  system lost energy to the surrounding
Work done on a system: Gas system

Expansion: +ve
increase of volume
Initial state

Initial state
Compression: -ve
decrease in volume
Heat of a system: Endo- vs Exorthemic
∆𝑼 = 𝒒 + 𝒘
q = +ve when the system absorbs heat energy (endothermic)
q = -ve when the system releases heat energy (exothermic)
w = +ve when work is done on the system
w = -ve when work is done by the system
Imagine a system with an initial internal energy (Uinitial). Then system
undergoes a change (work being done/heat transferred). After the
change, the final internal energy of the system is Ufinal.

Change in internal energy is defines as: ∆U = Ufinal-Uinitial

 NB: Make sure you
Examples: use the correct
sign!!!
1. 100 J of work is done on a system causing the internal energy of a system to increase by 74 J. How
much of the energy is transferred as heat? Also indicate direction.
∆U = Q + W, Q = ∆U – W, Q = 74 – 100, Q = -26 J (heat is lost in the process)
As 100 J of work is done to the system, only 74 J is used to increase internal energy, while 26 J is lost as
heat energy.

2. A sample of gas does 150 J of work against its surroundings and loses 90 J on internal energy in the
process. Does the gas gain or loose heat, and how much?
Q = ∆U – W, Q = -90 –(-150) = -90+150 = 60 J (Heat gained)

3. Gases A(g) and B(g) are confined in a cylinder-and-piston arrangement like that in Figure 5.4 and
react to form a solid product C(s): A1 (g) + B (g)  C (s). As the reaction occurs, the system loses 1150 J
of heat to the surroundings. The piston moves downward as the gases react to form a solid. As the
volume of the gas decreases under the constant pressure of the atmosphere, the surroundings does
480 J of work on the system. What is the change in the internal energy of the system? (Ans: -670 J)
 Reversible
Can be reversed to original state by exactly reversing the
process.
Carried out very slowly. Always at (or very close) equilibrium
Brought back to initial state without changing surrounding (no
temperature or pressure change)
Irreversible
Cannot be reversed (undone) by exactly reversing the change
in the system. Must take alternative pathway.
Carried out rapidly. Equilibrium obtained after completion.
Cannot be brought back to initial state without changing the
surrounding

Ideal (real world processes are irreversible) Real Processes

Equilibrium is a state of rest or balance due to equal action of opposing force

Chemical Equilibrium: Process where a forward reaction and reverse reaction take
place at the same rate. A Very Slow increase in
temperature
“maintains” the system
in equilibrium
For a reversible Process: A cylinder must be pulled or pushed slowly enough that the
system remains in thermal equilibrium
A: Reversible

A B

B:Irreversible

A B
Work done on an ideal gas
Pressure-Volume Work done on gas
Pressure is force exerted by the gas when it expands/compress
Force applied 𝑭
to expand gas
Define Pressure: P =
𝑨
F = P.A
Work is defined as force applied over a distance (x)
W = F.x
W = P.A.x
Introduce change in volume ∆V (V = A.x)
W = P. ∆V
Written as 𝒅𝒘 = − ‫( 𝑽𝒅𝑷 ׬‬negative work done by the gas)
• The work involved in the expansion or compression of gases is called pressure volume work
• Best visualized as a volume change of a gas in a cylinder with a movable piston.
• The pressure pushing down (or up) on the piston has some force (F) per area (A).
• As the gas expands the piston is pushed upward and this requires some energy (a force acting across a
distance).
• Note: As a matter of convention, negative work occurs when a system does work on the surroundings.
When the gas does work the volume of a gas increases ( Δ V > 0) and the work done is negative. Negative
work removes energy from the system. Positive work adds energy to the system.
Expansion Work: Scenarios
• General Expression:

• Work done on a gas at constant external Pressure (Pext):

NOTE!!!
Work done on the gas:
If ∆V = negative (compression)
Then w = +ve (gains energy)

Work done by the gas:

If ∆V = positive (expansion)
Then w = -ve (loses energy)
Expansion Work: Scenarios
• Work done on a gas at constant Pressure (Pint):
W= −P ‫ ׬‬dV = -Pint (V2 – V1)
𝑛𝑅𝑇
But V =
𝑃
𝑛𝑅𝑇2 𝑛𝑅𝑇1
w= -Pint ( – )
𝑃2 𝑃1

𝑛𝑅𝑇2 𝑛𝑅𝑇1
w = -Pint ( – ) [Pint = P1 = P2]
Pint Pint

= -nR(T2-T1)

• Work done on a ideal gas during a reversible process at constant V

W= −P ‫ ׬‬dV (dV = 0)
Therefore w = 0
Expansion Work: Scenarios
Important: ∆U = Q + W (∆U = 0)
Q = -W
• Work done on a ideal gas during a reversible
process at constant T
Expansion Work: Scenarios
• Work done on a ideal gas during a free expansion process
 Summary:

Work at constant P W = -Pint (Vf – Vi) = -R(T2-T1) P = Pint

Examples: Work done on a gas
1. 1 Mol ideal gas is compressed from 30 L to 10 L against a constant
external pressure of 3 atm. Derive a formula and calculate how much
work w is done on the system. (Ans: 6080 J)

2. One mole ideal gas is reversibly cooled down at constant V from

298 K to 149 K; then it is compressed isothermal from 20 L to 5 L; then
it is heated reversibly at constant V from 149 K to 298 K. Determine
the work done on the system. (NB: Work done depends on the path –
work a path function) Hint: Convert L  m3
Remember: Total work done w = w1 + w2 + w3 ….
 Physical Chemistry II
(CHE26M1)

Lecture #2b:
st
1 Law of
Thermodynamics
To be posted as a pre-recorded lecture