FIRST LAW OF THERMODYNAMICS I

Intended Learning Outcomes – after this lecture you will learn:

1. internal energy 𝑈𝑈 of a thermodynamic system
2. first law of thermodynamics
3. work done 𝑊𝑊 during volume change (pdV work)
4. path-dependence of heat 𝑄𝑄
Textbook Reference: Ch 19.1 – 19.4

A thermodynamic system is one that has the potential to

exchange energy with its surrounding

Such energy exchange can be in the form of heat Q and

work done W

Sign convention:
Q > 0 if heat flows into the system, < 0 if flows out of the
system
W > 0 if work done by the system, < 0 if work done on the
system

An everyday life example:

work done by system 𝑊𝑊 > 0 to lift the cover

system (popcorn)

stove provides heat 𝑄𝑄 > 0

An isolated system is one which does not exchange anything with its surrounding environment,
in particular, 𝑄𝑄 = 𝑊𝑊 = 0

A thermodynamic process is a process that changes the state (such as p, V, T) of a

thermodynamic system
While going from initial to final state, need to go through intermediate states, called a path

PHYS1112 Lecture 21 First Law of Thermodynamics I P. 1

A cyclic process is one whose initial and final states are the same
Internal energy U of a system is the sum of KE, and PE due to interaction among its constituent
particles
U does not include PE due to external interaction (such as gravitational PE due to the earth
on a gas)
𝑓𝑓
For an ideal gas, 𝑈𝑈 = 2 𝑁𝑁𝑁𝑁𝑁𝑁 ∝ 𝑇𝑇
𝑈𝑈 usually (but not always) increases with T

First Law of Thermodynamics

𝑄𝑄 = ∆𝑈𝑈 + 𝑊𝑊
generalization of conservation of energy to include heat

For an infinitesimal change of state, first law becomes

𝑑𝑑𝑑𝑑 = 𝑑𝑑𝑑𝑑 + 𝑑𝑑𝑑𝑑

∆𝑈𝑈 = 𝑄𝑄 − 𝑊𝑊 can be used as an operational definition of 𝑈𝑈 because both 𝑄𝑄 and 𝑊𝑊 can be

measured. No need to refer to KE or PE of microscopic particles
𝑈𝑈 is very much like a PE (of a conservative force) in that:
• 𝑈𝑈 is defined up to a constant, i.e., need an arbitrary zero level, like gravitation PE
• 𝑈𝑈 is experimentally found to be a state function, i.e., it depends on the
thermodynamic state (such as p, V, T) only , but not on the path
- Hence, for a cyclic process, ∆𝑈𝑈 = 0
- Equivalently, for fixed initial and final state, ∆𝑈𝑈 is path independent
But 𝑈𝑈 is not just the PE of constituent particles

Example 19.3 P. 649 A cyclic process

The process aba is a cyclic process
Given: 𝑊𝑊 = −500 J

𝑄𝑄 = ∆𝑈𝑈 + 𝑊𝑊 = 0 + (−500 J)
= −500 J
i.e., in this process external pressure does 500 J of
work on the system, and the process gives out 500 J of
heat

PHYS1112 Lecture 21 First Law of Thermodynamics I P. 2

Work
Work is the form of energy exchange which can be accounted for macroscopically
For example, work done during volume changes of a gas
work done by system against external pressure in an
infinitesimal volume change
𝑑𝑑𝑑𝑑 = 𝐹𝐹𝐹𝐹𝐹𝐹 = 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 = 𝑝𝑝𝑝𝑝𝑝𝑝
p always push outwards, i.e., p > 0
expansion, 𝑑𝑑𝑑𝑑 > 0, ∴ 𝑑𝑑𝑑𝑑 > 0 – work done by the gas
on the surrounding
compression , 𝑑𝑑𝑑𝑑 < 0, ∴ 𝑑𝑑𝑑𝑑 < 0 – work done on the
gas by the surrounding
work done in a finite volume change
𝑉𝑉2 area under the curve in a pV diagram, sometimes
𝑊𝑊 = � 𝑝𝑝𝑝𝑝𝑝𝑝 called 𝒑𝒑𝒑𝒑𝒑𝒑 work
𝑉𝑉1
note the sign and the initial and final volume

Example 19.1 P. 644

Suppose an ideal gas changes volume at constant pressure
𝑉𝑉2
𝑊𝑊 = � 𝑝𝑝𝑝𝑝𝑝𝑝 = 𝑝𝑝(𝑉𝑉2 − 𝑉𝑉1 )
𝑉𝑉1
at constant temperature
𝑉𝑉2 𝑉𝑉2
𝑛𝑛𝑛𝑛𝑛𝑛 𝑉𝑉2 𝑝𝑝1
𝑊𝑊 = � 𝑝𝑝𝑝𝑝𝑝𝑝 = � 𝑑𝑑𝑑𝑑 = 𝑛𝑛𝑛𝑛𝑛𝑛 ln = 𝑛𝑛𝑛𝑛𝑛𝑛 ln
𝑉𝑉1 𝑉𝑉1 𝑉𝑉 𝑉𝑉1 𝑝𝑝2

Question: is 𝑊𝑊 a state function?

PHYS1112 Lecture 21 First Law of Thermodynamics I P. 3

 From same initial state to same final state along
different paths
Areas under the paths are different
work done is path-dependent
W is not a state function

Example
An ideal gas. Suppose the initial state 1 and the final state 2 have the same
temperature, find W142, W132, and W12 along isotherm.

W14 = 0 since no volume change

W42 = p2(V2 – V1)
So W142 = W14 + W42 = p2(V2 – V1)

W13 = p1(V2 – V1)

W32 = 0 since no volume change
So W132 = W13 + W32 = p1(V2 – V1)

𝑉𝑉2 𝑝𝑝1
𝑊𝑊12 along isotherm = 𝑛𝑛𝑛𝑛𝑛𝑛 ln = 𝑛𝑛𝑛𝑛𝑛𝑛 ln
𝑉𝑉1 𝑝𝑝2

Heat
Heat is the form of energy exchange which cannot be accounted for macroscopically (as contrary
to work)
For example, boiling water by fire
Since ∆U is path-independent
W is path-dependent
By first law, 𝑄𝑄 = Δ𝑈𝑈 + 𝑊𝑊
heat is path-dependent
Q is not a state function

PHYS1112 Lecture 21 First Law of Thermodynamics I P. 4

Example
Suppose the initial state 1 and the final state 2 have the same
temperature, find Q142, Q132, and Q12 along isotherm.

Ideal gas internal energy depends on temperature only

Same temperature  ∆U = 0
By first law, Q = ∆U + W = W
Q142 = W142 = p2(V2 – V1)
Q132 = W132 = p1(V2 – V1)
𝑉𝑉2 𝑝𝑝1
𝑄𝑄12 along isotherm = 𝑊𝑊12 along isotherm = 𝑛𝑛𝑛𝑛𝑛𝑛 ln = 𝑛𝑛𝑛𝑛𝑛𝑛 ln
𝑉𝑉1 𝑝𝑝2

Example 19.4 P. 650

Given: ∆𝑈𝑈𝑎𝑎𝑎𝑎 = 510 J

In process ab:
𝑊𝑊𝑎𝑎𝑎𝑎 = 0 since no volume change
In process bd:
𝑊𝑊𝑏𝑏𝑏𝑏 = 𝑝𝑝(𝑉𝑉2 − 𝑉𝑉1 ) = (8.0 × 104 Pa)(3.0 × 10−3 m)
= 240 J
So 𝑊𝑊𝑎𝑎𝑎𝑎𝑎𝑎 = 𝑊𝑊𝑎𝑎𝑎𝑎 + 𝑊𝑊𝑏𝑏𝑏𝑏 = 240 J
Hence in process abd:
𝑄𝑄𝑎𝑎𝑎𝑎𝑎𝑎 = ∆𝑈𝑈𝑎𝑎𝑎𝑎 + 𝑊𝑊𝑎𝑎𝑎𝑎𝑎𝑎 = 750 J

In process ac:
𝑊𝑊𝑎𝑎𝑎𝑎 = (3.0 × 104 Pa)(3.0 × 10−3 m) = 90 J
In process cd:
𝑊𝑊𝑐𝑐𝑐𝑐 = 0 since no volume change
So 𝑊𝑊𝑎𝑎𝑎𝑎𝑎𝑎 = 𝑊𝑊𝑎𝑎𝑎𝑎 + 𝑊𝑊𝑐𝑐𝑐𝑐 = 90 J
Hence in process acd:
𝑄𝑄𝑎𝑎𝑎𝑎𝑎𝑎 = ∆𝑈𝑈𝑎𝑎𝑎𝑎 + 𝑊𝑊𝑎𝑎𝑎𝑎𝑎𝑎 = 600 J

Example 19.5 P. 651

1 g of water (1 cm3) becomes 1671 cm3 of steam when boiled at a constant pressure of 1 atm
(1.013 × 105 Pa). The heat of vaporization at this pressure is 𝐿𝐿𝑣𝑣 = 2.256 × 106 J/kg.
𝑊𝑊 = (1.013 × 105 Pa)(1670 × 10−6 m3 ) = 169 J
𝑄𝑄 = 𝑚𝑚𝐿𝐿𝑣𝑣 = (10−3 kg)(2.256 × 106 J/kg) = 2256 J
∆𝑈𝑈 = 𝑄𝑄 − 𝑊𝑊 = 2087 J

PHYS1112 Lecture 21 First Law of Thermodynamics I P. 5

Clicker Questions

Ans: Q19.1) A, Q19.4) B

PHYS1112 Lecture 21 First Law of Thermodynamics I P. 6

PHYS1112 Lecture 21 First Law of Thermodynamics I P. 7
For more detail see http://en.wikipedia.org/wiki/James_Prescott_Joule

PHYS1112 Lecture 21 First Law of Thermodynamics I P. 8