Chapter 1

THERMODYNAMICS
 IDEAL GAS EQUATION
𝑚𝑡𝑜𝑡
Obeys the equation: 𝑛=
PV = nRT 𝑀
P = Absolute Pressure (Atm , Pa)
V = Volume (m3, L ) If n = constant, then nR = constant
n = no. of moles of gas PV = nRT ⤑ ∆(PV) = nR∆T
T = Temperature in Kelvin (K)
R = Universal gas constant
𝑃𝑉
= 𝑛𝑅 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
= 8.314 J/mol.K 𝑇
= 0.0821 L.atm/mol.K
𝑃1 𝑉1 𝑃2 𝑉2
=
𝑇1 𝑇2
Ideal gas
• At constant volume:
𝑃 𝑛𝑅
• At constant temperature:. = = constant
𝑃𝑉 = 𝑛𝑅𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇 𝑉
✓Pressure is directly proportional
✓Pressure P is inversely to the temperature
proportional to the volume V
✓As the temperature increases,
✓As the volume increases, pressure also increases
pressure decreases.
✓As the temperature decreases,
✓As the volume decreases, pressure also decreases
pressure increases.
𝑃1 𝑃2
𝑃1 𝑉1 = 𝑃2 𝑉2 =
𝑇1 𝑇2
Ideal gas
• At constant Pressure:

𝑉 𝑛𝑅
= = constant
𝑇 𝑃
✓The volume is directly proportional to temperature

𝑉1 𝑉2
=
𝑇1 𝑇2
Molar heat capacities of an ideal gas
 Solution:
Example 1
• A 20.0-L tank contains 4.86x10-4kg of
helium at 18.00C. The molar mass of
helium is 4.00 g/mol
(a) How many moles of helium are in
the tank?
(b) What is the pressure in the tank, in
pascals and in atmospheres?
Example 2 Solution:

A 3.00-L tank contains air at 3.00 atm and 20.00C. The

tank is sealed and cooled until the pressure is 1.00
atm.
(a) What is the temperature then in degrees Celsius?
Assume that the volume of the tank is constant.

(b) If the temperature is kept at the value found in

part (a) and the gas is compressed, what is the
volume when the pressure again becomes 3.00
atm?
Thermodynamics
 Thermodynamic system and process

✓Thermodynamic system ✓Thermodynamic process

▪ Any collection of objects that
can exchange energy with its
surroundings.
Ex: A gas in a cylinder with a
movable piston.
▪ Is defined as a change from one
state to another state.
▪ The initial and final states are the
defining elements of the process.
Work done during volume changes
• An expanding gas (system)
Work done during volume changes
✓At constant pressure:
𝑊 = 𝑝(𝑉2 − 𝑉1 ) From:

✓At constant temperature:

At constant volume:
W=0
 Work done on a PV - diagram

✓Work done W is equal to the area under the curve on a PV – diagram

(a) (b) (c)

Work done depends on the path chosen
Example 1

✓A gas undergoes two processes. In the first, the volume remains

constant at 0.200m3 and the pressure increases from 2.00x105Pa to
5.00x105Pa. The second process is a compression to a volume of
0.120m3 at a constant pressure of 5.00x105Pa.
(a) In a pV-diagram, show both processes.
(b) Find the total work done by the gas during both processes.
Solution
Example 2
✓ A quantity of air is taken from state a to state b along a path that is a straight line in the pV-diagram shown
below. If Va = 0.070m3 , Vb = 0.110m3, Pa = 1.00x105 Pa, and Pb = 1.40x105 Pa. what is the work W done by
the gas in this process? Assume that the gas may be treated as ideal.

Solution:
Internal Energy
The First Law of Thermodynamics
Sample 1
Solution
Sample 2
Solution
 Kinds of thermodynamic processes
1. Isochoric process – Constant volume process
W=0 Q = ∆U + W 𝑄 = ∆𝑈 = 𝑛𝐶𝑣 ∆𝑇 𝑃𝑉 = 𝑛𝑅𝑇 ⤑ ∆(𝑃𝑉) = 𝑛𝑅(∆𝑇)

2. Isobaric process – Constant pressure process

𝑊 = 𝑝(𝑉2 − 𝑉1 ) Q = ∆U + W 𝑄 = 𝑛𝐶𝑣 ∆𝑇 + 𝑝(𝑉2 − 𝑉1 )
𝑃𝑉 = 𝑛𝑅𝑇

3. Isothermal process – Constant temperature process

𝑉2 𝑃1
∆𝑈 = 0 𝑄 = 𝑊 = 𝑛𝑅𝑇 𝑙𝑛 𝑉 = 𝑛𝑅𝑇 𝑙𝑛 𝑃 𝑃𝑉 = 𝑛𝑅𝑇
1 2

4. Adiabatic process – No heat flows into or out of the system.

𝑄=0 𝑄 = ∆𝑈 + 𝑊 𝑊 = −∆𝑈 = −𝑛𝐶𝑣 ∆𝑇 𝑃𝑉 = 𝑛𝑅𝑇
The 4 processes on a PV - diagram
Adiabatic process for an ideal gas
 Solution:
Example 1:
✓A monatomic ideal gas that is
initially at a pressure of
1.50x105Pa and has a volume
of 0.080m3 is compressed
adiabatically to a volume of
0.040m3
(a) What is the final pressure?
(b) How much work is done by
the gas?
Example 2
✓ A monatomic ideal gas expands slowly to twice its original volume, doing 300 J of work in the process. Find
the heat added to the gas and the change in internal energy of the gas if the process is (a) isothermal; (b)
adiabatic; (c) isobaric.
 nd
Heat Engines and the
2
Law of Thermodynamics
Heat Engines
✓Heat engine - A device that transforms heat partly into work by a working substance
undergoing a cyclic process.
▪ Examples of working substance :
o Internal combustion engine – a mixture of air and fuel
o Steam turbine – water

✓For any cyclic process:

∆𝑈 = 0 𝑎𝑛𝑑 𝑄 = 𝑊
✓ All heat engines absorb heat from a source (Hot reservoir) at a relatively high
temperature, perform some mechanical work, and discard or reject
some heat at a lower temperature (Cold reservoir) .
Flow diagram of a heat engine
 Power station as a heat engine
• Heat coming from a combustion or
nuclear reaction is fed into the circuit
in a boiler, where the medium is
vaporized,
(i.e. liquid water is turned into
high-pressure steam.)
• The pressurized steam drives a
turbine, producing work, which can be
used to drive a generator producing
electricity
• After the turbine, the pressure of the
steam will be reduced.
• The gas is fed through a condenser, a
section of pipe with diathermal walls
where heat can pass through to the
surroundings (e.g. through a cooling
tower or nearby river).
• Here the gas is transformed back into
a liquid which is then pumped back
into the boiler to complete the cycle.
 Thermal efficiency e of a heat engine

✓Thermal efficiency ✓In a heat engine, Qc can never

represents the fraction of be zero (there is always heat
𝑄𝐻 that is converted to work rejected)
W. ✓No heat engine is 100% efficient
(There is no perfect engine)
𝑊
𝑒= ✓Heat added cannot all be
𝑄𝐻
converted to useful work. That
is,
𝑄𝐶 𝑄𝐻 ≠ 𝑊
𝑒 =1−
𝑄𝐻
 The 2nd law of the thermodynamics
(The engine statement of the second law)

✓ “It is impossible for any system to undergo a process in which it

absorbs heat from a reservoir at a single temperature and
converts the heat completely into mechanical work, with the
system ending in the same state in which it began”.

➢ Also called the Kelvin – Planck statement of the 2nd law of

thermodynamics
Sample problem
Solution
Carnot engine
 Thermal efficiency of Carnot engine

𝑊
𝑒=𝑄
𝐻
𝑄𝐶
𝑒 =1− 𝑄𝐻
Example
A Carnot engine takes 2000 J of heat from a reservoir at 500 K, does some work, and discards some heat to a
reservoir at 350 K. A.) How much work does it do, B) how much heat is discarded, C) and what is its efficiency?
Refrigerator
▪ A heat engine that takes heat from a cold place (inside of the refrigerator) and gives it off to a
warmer place
▪ An engine operating in reverse
▪ Requires a net input of mechanical work
✓ Energy flow diagram for a refrigerator
Example
✓ A refrigerator has a coefficient of performance of 2.10. In each cycle it absorbs 3.40x104 J of heat from the
cold reservoir.
(a) How much mechanical energy is required each cycle to operate the refrigerator?
(b) During each cycle, how much heat is discarded to the high-temperature reservoir?
 The 2 nd law of the thermodynamics
(The refrigerator statement of the second law)

✓ “It is impossible for any process to have as its sole result

the transfer of heat from a cooler to a hotter body”.

➢ Also known as the Clausius statement of this law

Entropy and the Second law
of Thermodynamics