UNIT 10 15.

1
15.2
Chapter 15 15.3
Thermodynamics
Slide 1
15.1 THE FIRST LAW OF
THERMODYNAMICS

Joule’s
Experiment

“… wherever mechanical
force is expended, an exact
equivalent of heat is always
obtained” —
J.P. Joule, August, 1843

Slide 2
 15.1 THE FIRST LAW OF
THERMODYNAMICS
Both work and heat can change the internal energy of a system.

These two methods of changing the internal energy of a system

lead to the first law of thermodynamics.

First Law of Thermodynamics

The change in internal energy of a system is equal to the heat

flow into the system plus the work done on the system.

Slide 3
 15.1 THE FIRST LAW OF
THERMODYNAMICS

When a gas is compressed, the work done is positive.

When a gas expands, the work done is negative .

The pressure exerted by the gas is the force exerted per unit area:
𝐹
𝑃=
𝐴
Slide 4
15.1 THE FIRST LAW OF
THERMODYNAMICS

Slide 5
Example
In part (a) of figure, the system gains 1500J of heat and
2200J of work is done by the system on its surroundings.

In part (b), the system also gains 1500J of heat, but 2200J
of work is done on the system.

In each case, calculate the change in internal energy

of the system.

Slide 6
Example
In part (a) of figure, the system gains 1500J of heat and
2200J of work is done by the system on its surroundings.

In part (b), the system also gains 1500J of heat, but 2200J
of work is done on the system.

In each case, calculate the change in internal energy

of the system.

SOLUTION

(a) U  Q  W   1500 J    2200 J   700 J

(b) U  Q  W   1500 J    2200 J   3700 J

Slide 7
 15.2 THERMODYNAMIC PROCESSES
A thermodynamic process is the method by which a system is changed
from one state to another. The state of a system is described by a set of
state variables such as pressure (P), temperature (T), volume (V),
number of moles (n), and internal energy (E).

THERMODYNAMIC PROCESSES

isobaric: constant pressure

isochoric: constant volume

isothermal: constant temperature

adiabatic: no transfer of heat

Slide 8
15.2 THERMODYNAMIC PROCESSES
Work done on a gas
Work done by gas on piston:
𝑊 = 𝐹 ∙ ∆𝑟 = 𝐹 ∆𝑟 cos 0 = 𝐹 ∆𝑟
But pressure of gas is:
𝐹
𝑃= , ∴𝐹=𝑃𝐴 𝐹 ∆𝑟
𝐴

∴ 𝑊 = 𝑃 𝐴 ∆𝑟 = 𝑃∆𝑉
(work done by gas on plunger)

So work done on gas:

∴ 𝑊 = −𝑃 ∆𝑉

Slide 9
 15.2 THERMODYNAMIC PROCESSES
The PV Diagram
For a graph of the pressure versus the volume of an enclosed
gas, the work done on the gas is given by the area under the
curve, or the area under the Pressure-Volume function, P(V),
which is called a P - V diagram.

The magnitude of the total work

done on the gas is the area under
the PV curve.

W   P  V   PV f  Vi 
Slide 10
Sign of work done on gas
During an increase in volume, ΔV is positive and the work done (on
the gas) is negative. W  0  Vinitial  V final

During a decrease in volume, ΔV is negative and the work done (on

the gas) is positive.
W  0  Vinitial  V final

W   P  V   PV f  Vi 

Slide 11
Work Done During a Closed Cycle
Example
Sketch a PV diagram and find the
work done on the gas during
the following stages:

(a) A gas is expanded from a

volume of 1.0 L to 3.0 L at a
constant pressure of 3.0 atm.
WON   PV  3x105 (0.003  0.001)  600 J
(b) The gas is then cooled at a
constant volume until the
pressure falls to 2.0 atm

W   PV  0
since V  0

Slide 12
Example Continued

(c) The gas is then compressed

at a constant pressure of 2.0 atm
from a volume of 3.0 L to 1.0 L.

WON   PV  2 105 (0.001  .003)  400 J

(d) The gas is then heated until

its pressure increases from 2.0 atm
to 3.0 atm at a constant volume.

W   PV  0
since V  0

Slide 13
Example Continued
What is the
NET WORK DONE
ON THE SYTEM? NET work is
the area inside
600 J + 400 J = 200 J the shape.

Rule of thumb: If the system rotates

Clock Wise (CW), the NET work is
negative.

If the system rotates Counter-Clock Wise

(CCW), the NET work is positive.

Slide 14
INTERNAL ENERGY OF AN IDEAL GAS
Real gases behave like ideal gases in certain circumstances. An
ideal gas (which obeys the ideal gas law) has certain properties,
for example:

Gas particles are identical, all collisions between particles are

elastic, there are no intermolecular forces between the gas
particles, etc.

As a results of these properties;

The internal energy of an ideal gas (𝑈) ONLY depends on the

temperature of the gas (𝑇). If there is no temperature change,
there will be no change in internal energy (∆𝑈 = 0).

Slide 15
 15.2 THERMODYNAMIC PROCESSES
Constant-Pressure Processes: ISOBARIC
A process by which the state of a system is changed while the pressure
is held constant is called an isobaric process.

Slide 16
Constant-Volume Processes: ISOCHORIC
A process by which the state of a system is changed while the volume
remains constant is called an isochoric process.
isochoric: constant volume
W   PV   PV f  Vi 
But V f  V i = 0 since V f = Vi
No work is done for an isochoric process!

W 0
U  Q  W
U  Q

Slide 17
 15.2 THERMODYNAMIC PROCESSES
Constant-Temperature Processes: ISOTHERMAL
A process in which the temperature of the system remains constant is
called an isothermal process.

Vf 
Does not hold for isothermal process!
W  nRT ln  
 Vi 
Recall: The internal energy of an ideal gas (U) ONLY depends on the temperature of the gas
(T). If there is no temperature change, there will be no change in internal energy.

So for isothermal process: ∆𝑈 = 0

The change in the internal energy of an ideal gas undergoing
isothermal expansion or compression is zero, thus from first law of
thermodynamics for a closed system it follows that:
Q = −𝑊
Slide 18
 15.2 THERMODYNAMIC PROCESSES
No heat transfer: ADIABATIC PROCESS
A process in which no heat is transferred into or out of the system is
called an adiabatic process.

NB: An adiabatic process is not the same as a constant-temperature

(isothermal) process. In an isothermal process, heat flow into or out of
a system is necessary to maintain a constant temperature. In an
adiabatic process, no heat flow occurs, so if work is done, the
temperature of the system may change.

Slide 19
15.2 THERMODYNAMIC PROCESSES

Slide 20
MOLAR SPECIFIC HEAT CAPACITY

• Heat capacity: 𝑪
𝑪
• Specific heat capacity: 𝑐=
𝒎
• Molar specific heat capacity (applicable to ideal gasses):
The amount of heat in joules required to raise 1 mole of a
substance by 1 Kelvin

𝑪
Constant pressure: 𝑪𝑷 = , 𝐐 = 𝒏 𝑪𝒑 ∆𝑻
𝒏

𝑪
Constant volume: 𝑪𝑽 = , 𝐐 = 𝒏 𝑪𝒗 ∆𝑻
𝒏

Slide 21
 15.3 THERMODYNAMIC PROCESSES
FOR AN IDEAL GAS
Constant-Pressure Processes: ISOBARIC

𝑄 = 𝑛 𝐶𝑝 ∆𝑇 (constant pressure)
∆𝑈 = 𝑄 + 𝑊 first law; always holds
Using the First Law and ideal gas law for isobaric processes, it can
be shown that:

𝐶𝑣 = 𝐶𝑝 − 𝑅 (always holds for ideal gas)

Slide 22
Constant-Volume Processes: ISOCHORIC

W 0
U  Q  W
U  Q
𝑅𝑒𝑐𝑎𝑙𝑙 𝑓𝑜𝑟 𝑖𝑠𝑜𝑏𝑎𝑟𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠:
𝑄 = 𝑛 𝐶𝑣 ∆𝑇
∴ ∆𝑈 = 𝑛 𝐶𝑣 ∆𝑇
(always holds for ideal gas,
since U only depends on temperature)
3 5
For a monatomic gas: 𝐶𝑣 = 2 𝑅 For a diatomic gas: 𝐶𝑣 = 2 𝑅
𝟑 𝟓
∴ ∆𝑼 = 𝒏𝑹 ∆𝑻 ∴ ∆𝑼 = 𝒏𝑹 ∆𝑻
𝟐 𝟐

Slide 23
15.3 THERMODYNAMIC PROCESSES
FOR AN IDEAL GAS
Constant Temperature: ISOTHERMAL

At constant temperature we have that

𝑉𝑖 𝑃𝑓
𝑃𝑖 𝑉𝑖 = 𝑃𝑓 𝑉𝑓 =
𝑉𝑓 𝑃𝑖

 Pf 
W  nRT ln  
 Pi 
Slide 24
 SUMMARY

Ideal gas law:

𝑃𝑉 = 𝑛𝑅𝑇
First Law of Thermodynamics:
∆𝑈 = 𝑄 + 𝑊
Internal energy of ideal gas:
∆𝑈 = 𝑛 𝐶𝑣 ∆𝑇
Molar specific heat capacity:
𝐶𝑣 = 𝐶𝑝 − 𝑅

Slide 25
 SUMMARY (CONTINUED)
Isochoric process:
𝑊=0
𝑄 = 𝑛 𝐶𝑣 ∆𝑇
Isobaric process:
𝑊 = −𝑃 ∆𝑉
𝑄 = 𝑛 𝐶𝑝 ∆𝑇
Isothermal process:
𝑉𝑓 𝑉𝑖
𝑊 = −𝑛𝑅𝑇 ln = 𝑛𝑅𝑇 ln
𝑉𝑖 𝑉𝑓
∆𝑈 = 0
Adiabatic process:
𝑄=0
Slide 26
 SUMMARY (CONTINUED)
Monatomic ideal gas:
3
𝐶𝑣 = 𝑅
2
3
∆𝑈 = 𝑛𝑅∆𝑇
2

Diatomic ideal gas:

5
𝐶𝑣 = 𝑅
2
5
∆𝑈 = 𝑛𝑅∆𝑇
2

Slide 27
Example 15.3
An ideal gas is kept in thermal contact with a heat reservoir at 7°C
(280 K) while it is compressed from a volume of 20.0 L to a volume of
10.0 L. During the compression, an average force of 33.3 kN is used to
move the piston a distance of 0.15 m. (a) Calculate how much heat is
exchanged between the gas and the reservoir. (b) Does the heat flow
into or out of the gas?

Slide 28
Example 15.3
Solution
(a)

(b) Since positive Q represents heat flow into the gas, the negative
sign tells us that heat flows out of the gas into the reservoir.

Slide 29
ADDITIONAL EXAMPLES
Example A
One gram of water is placed in the
cylinder and the pressure is maintained at
2.0×105 Pa. The temperature of the water
is raised by 31C. The water is in the
liquid phase and expands by the small
amount of 1.0×10-8m3.
Calculate the work done and the change
in internal energy. [Specific heat of water
is 4186 J/(kg.C)

Slide 30
 Solution
W   PV
 2.0  105 Pa 1.0  108 m3   0.0020J

U  Q  W  129.766 J  0.002 J  129.764J

   
Q  mcT  0.001 kg  4186 J kg  C 31 C  129.766 J

Slide 31
Example B
Two moles of the monatomic gas argon expand
isothermally at 298K from and initial volume of
0.025m3 to a final volume of 0.050 m3. Assuming that
argon is an ideal gas, find (a) the work done by the
gas, (b) the change in internal energy of the gas, and
(c) the heat supplied to the gas.

Slide 32
SOLUTION
(a) V f 
W  nRT ln 

 Vi 
 0.050 m 3 
 2.0 mol8.31 J mol  K 298 K  ln   3400 J
 0.025 m 3 
 

(b) U  32 nRT f  32 nRTi  0

(c) U  Q  W
Q  W   3400 J   3400 J

Slide 33
Example C
Calculate the work for an isothermal expansion between pi = 1 atm
and pf = 0.1 atm for 10 mol of an ideal gas at temperature 0C.

SOLUTION: For an isothermal process:

Vinitial 
W  nRT ln  
 final 
V
Therefore:
 PFINAL 
W  nRT ln  
 PINITIAL 

J  0.1
W  (10mol )(8.314 )(273K ) ln    52.3kJ
K  mol 1.0 

Slide 34
 SELF ASSESSMENTS
EXAMPLE (A)
A system does 164 J of work on its environment and gains 77 J of heat
in the process. Calculate the change in the internal energy of the
system.
EXAMPLES (B)
Three moles of an ideal monatomic gas are at a temperature of 345 K.
Then, 2438 J of heat is added to the gas, and 962 J of work is done on
it. Calculate the final temperature of the gas
EXAMPLE (C)
A piece of aluminum has a volume of 1.4 × 10-3 m3. The coefficient of
volume expansion for aluminum is  = 69 × 10-6 K-1. The temperature
of this object is raised from 20 to 320 °C. How much work is done by
the expanding aluminum if the air pressure is 1.01 × 105 Pa.

Slide 35
Example D:
When a rifle is fired, the expanding gas from the burning gunpowder creates a
pressure behind the bullet. This pressure causes the force that pushes the bullet
through the barrel. The barrel is cylindrical with a length of 0.61 m and an
opening with radius is 2.8 × 103 m. A bullet (mass = 2.6 × 103 kg) has a speed of
370 m/s just after leaving the barrel. Ignore friction and calculate the average
pressure of the expanding gas. [HINT: Assume that the expansion of the gas is
isobaric]

Slide 36
Example E:
A System consisting of 3.00 moles of an ideal monatomic
gas has a temperature of 345 K. There is
2438 J of heat transferred to the system, and 962 J of
work is done on it. Calculate the final temperature of the
system.

Slide 37
Example F
Suppose a monatomic ideal gas is changed from state A to C by first
following the constant pressure path A  B followed by the constant
temperature path B  C.
Calculate the heat
transferred to the gas
to change its state
from A to C.

Slide 38
End