2.

1 Introduction to the First Law

The first law of thermodynamics
• Conservation of energy principle - energy can be neither created nor destroyed;
it can only change forms

• Total energy of a system (Esystem) is the sum of three separate energies

𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = 𝐼𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 + 𝐾𝑖𝑛𝑒𝑡𝑖𝑐 𝐸𝑛𝑒𝑟𝑔𝑦 + 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 → 𝐸 = 𝑈 + 𝐾𝐸 + 𝑃𝐸

• Internal Energy (U): energy contained within molecules of system

– Translational, rotational, vibrational motion of molecules
– Also electric energy of atoms (intermolecular forces)

• Kinetic Energy (KE): energy related with motion of system

𝑉
𝑚𝑉 2
𝐾𝐸 = 𝑚𝑉𝑑𝑉 =
𝑉=0 2
• Potential Energy (PE): energy related to system elevation Δz
𝑧
𝑃𝐸 = 𝑚𝑔 𝑑𝑧 = 𝑚𝑔𝑧
𝑧=0 3
 2.1 Introduction to the First Law
• Conservation of energy principle (first law of thermodynamics) is expressed as:

𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑇𝑜𝑡𝑎𝑙 𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦

= −
𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑆𝑦𝑠𝑡𝑒𝑚 𝐸𝑛𝑡𝑒𝑟𝑖𝑛𝑔 𝑡ℎ𝑒 𝑆𝑦𝑠𝑡𝑒𝑚 𝐿𝑒𝑎𝑣𝑖𝑛𝑔 𝑡ℎ𝑒 𝑆𝑦𝑠𝑡𝑒𝑚

∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = 𝐸𝑖𝑛 − 𝐸𝑜𝑢𝑡

• ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚 : change in internal energy, kinetic energy and potential energy of the
system
– ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = ∆𝑈 + ∆𝐾𝐸 + ∆𝑃𝐸
1
– ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑚∆𝑢 + 2 𝑚∆𝑉 2 + 𝑚𝑔∆𝑧 (𝑘𝐽)
1
– ∆𝑒𝑠𝑦𝑠𝑡𝑒𝑚 = ∆𝑢 + 2 ∆𝑉 2 + 𝑔∆𝑧 (𝑘𝐽 𝑘𝑔)

• 𝐸𝑖𝑛 & 𝐸𝑜𝑢𝑡 : energy transfer that crosses the

boundary of a system
– Work: 𝑊𝑛𝑒𝑡 = 𝑊𝑖𝑛 − 𝑊𝑜𝑢𝑡
– Heat: 𝑄𝑛𝑒𝑡 = 𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡
– Mass
4
 2.1 Introduction to the First Law
Different forms of energy balance

• General: ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = 𝐸𝑖𝑛 − 𝐸𝑜𝑢𝑡 𝑘𝐽

𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑈,𝐾𝐸,𝑃𝐸 𝑁𝑒𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟
𝑏𝑦 ℎ𝑒𝑎𝑡,𝑤𝑜𝑟𝑘,𝑚𝑎𝑠𝑠

• Rate form: ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = 𝐸𝑖𝑛 − 𝐸𝑜𝑢𝑡 𝑘𝑊

𝑅𝑎𝑡𝑒 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑛𝑒𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟
𝑈,𝐾𝐸,𝑃𝐸 𝑏𝑦 ℎ𝑒𝑎𝑡,𝑤𝑜𝑟𝑘,𝑚𝑎𝑠𝑠

• For constant rates, the total quantities during the time interval t are related to the
quantities per unit time as
𝑄 = 𝑄 ∆𝑡 𝑊 = 𝑊 ∆𝑡 ∆𝐸 = ∆𝐸 ∆𝑡

• The energy balance may be expressed on a per unit mass basis as

1
• ∆𝑒𝑠𝑦𝑠𝑡𝑒𝑚 = ∆𝑢 + 2 ∆𝑉 2 + 𝑔∆𝑧 (𝑘𝐽 𝑘𝑔)

• 𝑒𝑖𝑛 − 𝑒𝑜𝑢𝑡 = 𝑞𝑛𝑒𝑡 − 𝑤𝑛𝑒𝑡 (𝑘𝐽 𝑘𝑔)

5
2.1 Introduction to the First Law
The energy balance for a general system is

∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = ∆𝑈 + ∆𝐾𝐸 + ∆𝑃𝐸 = 𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡 + 𝑊𝑖𝑛 − 𝑊𝑜𝑢𝑡 + 𝐸𝑚𝑎𝑠𝑠,𝑖𝑛 − 𝐸𝑚𝑎𝑠𝑠,𝑜𝑢𝑡

Types of thermodynamics systems for 1st law

• Closed (fixed mass) system: work and heat are only mechanisms of energy transfer at
the system boundary (i.e. no mass transfer)
• Open systems (control volumes): mass, work and heat can all cross system boundary

OPEN
SYSTEM

6
2.2 Energy transfer by work, heat, and mass
1. Work, W: Energy transfer at a system boundary that is
accounted for by forces exerted on the system by the
surroundings. When added to a system, the energy of the
system increases; and when done by a system, the energy
of the system decreases.

2. Heat Transfer, Q: Energy transfer caused by a temperature

difference between the system and its surroundings. Heat
transfer to the system causes the energy of a system to
increase and heat transfer from a system causes the energy
to decrease. Q is zero for adiabatic systems.

3. Mass flow: As mass flows into a system, the energy of the

system increases by the amount of energy carried with the
mass into the system. Mass leaving the system carries
energy with it, and the energy of the system decreases.
7
2.2.1 Energy transfer by work
Forms of Work 2
We   V I dt (kJ)
1
Electrical Work: electrical energy done by electrons crossing
the system boundary (e.g. electrical heater inside the system
(blue)). Note that the definition of the system boundary will
indicate if electrical work will be denoted as work or heat. If
heater is outside the boundary (red), energy will be transferred
as heat.
 
 W  F  d s  Fds cos
Mechanical Work: energy expended by a force, F, acting
through a distance, s. Common types: shaft work, spring
work, work done to raise or accelerate a body, and work to
move an object

Boundary work: type of mechanical work that we will treat

specially in thermodynamics. Work due to moving boundaries
of the system. Commonly seen in piston/cylinder devices as
gas expands or is compressed by an external force.

8
2.2.1 Energy transfer by work
Net Work Done By A Closed System

𝑊𝑛𝑒𝑡 = 𝑊𝑜𝑢𝑡 − 𝑊𝑖𝑛 + 𝑊𝑏𝑜𝑢𝑛𝑑𝑎𝑟𝑦

𝐸𝑙𝑒𝑐.+𝑀𝑒𝑐ℎ.

Example 2-1
A fluid contained in a piston- Wele =500 kJ Wb=600 kJ
cylinder device receives 500 kJ
Wnet  Wnet 
of electrical work as the gas
expands against the piston and  Wb
other

Wnet  Wout  Win, ele 

does 600 kJ of boundary work
on the piston. What is the net  Wb
other
work done by the fluid?
Wnet   0  500 kJ   600 kJ
Wnet  100 kJ 9
2.2.2 Moving Boundary Work
• Boundary work occurs because the mass of the substance contained within the
system boundary causes a force to act on the boundary surface and make the
boundary move.
2 2 2
• 𝑊𝑏 = 1
𝛿𝑊𝑏 = 1
𝐹𝑑𝑠 = 1
𝑃𝐴𝑑𝑠
2
• 𝑊𝑏 = 1
𝑃𝑑𝑉

• The area under the process curve on P-V diagram represents the boundary
work. P is the absolute pressure.
10
2.2.2 Moving Boundary Work
• Sign convention of boundary work
2 2
𝑊𝑏 = 𝛿𝑊𝑏 = 𝑃𝑑𝑉 System boundary
1 1

GAS
• If PA > F piston will move outwards
P
– Gas will expand; volume increase (+ dV)
2 A
– 𝑊𝑏 = 1
𝑃𝑑𝑉 is out of the system
• If PA < F piston will move inwards
F
– Gas will compress; volume decrease (- dV)
2
– 𝑊𝑏 = 1
𝑃𝑑𝑉 is into the system

• Is work in or out?
– Always draw a diagram of the system
– Draw forces from PA and from an external force F external to the system
– Work will point in the same direction as the larger force (PA or F)
11
2.2.2 Moving Boundary Work
• Piston/cylinder devices are common devices we will
study in Thermodynamics
– Example: vapor compression refrigeration System boundary

https://www.youtube.com/watch?v=fTDkG1y5R34 GAS

Expansion
Valve
HEAT
F

Evaporator
HEAT coils

Condenser
coils

Compressor

12
2.2.2 Moving Boundary Work
• Boundary work is process dependent; differential of boundary work Wb is called
inexact.
𝛿𝑊𝑏 = 𝑃𝑑𝑉
• Boundary work is a path function → the magnitude depends on the path followed
2
• 1
𝛿𝑊𝑏 = 𝑊21 (𝑛𝑜𝑡 ∆𝑊)

• Work is not a property of the system

– i.e. not W2-W1
700
• Path functions have inexact differentials (δ) kPa
– FYI: P,T,v,u,h,s are point functions –
depend only on the state

• Total amount of work is obtained by 100

following the process path and adding kPa
differential amounts of work (δW) along the
way (i.e. integration) 0.01 m3 0.03 m3

• The P-V relationship must be known

P  f (V ) 13
2.2.2 Moving Boundary Work
Common boundary work processes:

a) Constant volume P1 1
If the volume is held constant, dV = 0, and the P-V diagram for
boundary work equation becomes V = constant
P2 2

V =V
1 2
V

b) Constant pressure
If the pressure is held constant, the boundary 2 1
P1 = P2
work equation becomes
P-V diagram for
P = constant
V V V
1 2

14
2.2.2 Moving Boundary Work
Common boundary work processes:

c) Constant temperature, ideal gas

If the temperature of an ideal gas system is held constant, then the equation of state
provides the pressure-volume relation
• 𝑃𝑉 = 𝑚𝑅𝑇
𝑚𝑅𝑇
• 𝑃=
𝑉
2 2 𝑚𝑅𝑇
• 𝑊𝑏 = 1
𝑃𝑑𝑉 = 1 𝑉
𝑑𝑉
21
• 𝑊𝑏 = 𝑚𝑅𝑇 1 𝑉
𝑑𝑉
Note: For non-ideal gases undergoing an
𝑉2 isothermal (constant temperature) process,
• 𝑊𝑏 = 𝑚𝑅𝑇 𝑙𝑛
𝑉1 the integral in the boundary work equation
would be done numerically since the ideal
gas equation of state could not be used.

15
2.2.2 Moving Boundary Work
Common boundary work processes:
d) The polytropic process:
PV n  constant

The exponent (n) may have any value from positive infinity to negative infinity
depending on the process. Some of the more common values are given below.

Process Exponent (n)

Constant pressure 0
Constant volume  k is the ratio of the specific heats CP and CV.
(lecture 6)
Isothermal & ideal gas 1
Adiabatic & ideal gas k = CP/CV 16
2.2.2 Moving Boundary Work
Common boundary work processes:
d) The polytropic process: ... continued
• The boundary work done during the polytropic process is found by
substituting the pressure-volume relation into the boundary work equation.

𝑃𝑉 𝑛 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 == 𝑃1 𝑉1 𝑛 = 𝑃2 𝑉2 𝑛

For an ideal gas (n = 1) this result is equivalent to the isothermal process

discussed earlier.
17
2.2.2 Moving Boundary Work
Common boundary work processes:
e) Other P-v relationships Po
x
e.g. piston loaded with linear spring ks
g
• 𝐹𝑠𝑝𝑟𝑖𝑛𝑔 = 𝑘𝑠 𝑥; 𝑘𝑠 is the spring constant (N/m)
P
1 2
• 𝑊𝑠𝑝𝑟𝑖𝑛𝑔 = 𝐹𝑠𝑝𝑟𝑖𝑛𝑔 𝑑𝑥 = 𝑘𝑠 𝑥𝑑𝑥 = 𝑘 𝑠 𝑥
2

• 𝐹 = 𝑃 ∗ 𝐴 = 𝑘𝑠 𝑥; 𝑉 =𝐴∗𝑥
P
𝑘 𝑘𝑠
• 𝑃 = 𝐴2𝑠 𝑉  linear relationship between P and V 𝐴2
P2
.
• ∆𝑃 ∆𝑉 = 𝑘𝑠 𝐴2
2
P1 . 𝑊21
• 𝑊𝑏𝑜𝑢𝑛𝑑𝑎𝑟𝑦 = 1
𝑃𝑑𝑉 = 𝑎𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑃 − 𝑉 𝑐𝑢𝑟𝑣𝑒
1 V
• 𝑊𝑏𝑜𝑢𝑛𝑑𝑎𝑟𝑦 = 𝑃1 + 𝑃2 ∗ 𝑉2 − 𝑉1 V1 V2
2

• Notice that the spring work may not equal the

work done by/on the system
18
2.2.2 Moving Boundary Work
Example 2.2
A cylinder equipped with an linear spring is filled with air with 200 kPa and volume 0.2m3.
Initially the spring is in contact with the piston, but does not exert any force on it. Heat is
transferred to the air to a final pressure of 800 kPa and 0.5 m3. What is the final work done
by the system? What is the work done by the spring?
Solution: Po
2
𝑊𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑃𝑑𝑉 = 𝑎𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑃 − 𝑉 𝑐𝑢𝑟𝑣𝑒 x
ks
1
1 g
𝑊𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑃1 + 𝑃2 ∗ 𝑉2 − 𝑉1 = 150𝑘𝐽
2
P
If there were no spring, pressure would be constant at 200
P Q
kPa as the piston rises (i.e. force needed to overcome
piston is constant). .
2 P2
𝑊𝑛𝑜 𝑠𝑝𝑟𝑖𝑛𝑔 = 𝑃𝑑𝑉 = 𝑃 𝑉2 − 𝑉1 = 60kJ 2
1 .
P1
𝑊𝑠𝑝𝑟𝑖𝑛𝑔 = 𝑊𝑠𝑦𝑠𝑡𝑒𝑚 − 𝑊𝑛𝑜 𝑠𝑝𝑟𝑖𝑛𝑔 = 90𝑘𝐽
2
V
V1 V2
19
2.2.3 Energy transfer by heat
• Heat: energy transfer caused by a temperature difference between the system and
the surroundings
• Units: joules (J) or kilojoules (kJ) Qin
• The net heat transferred to a system: Qout

𝑄𝑛𝑒𝑡 = 𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡

• Qin and Qout are magnitudes of heat transfer values

• Heat transfer per unit mass: 𝑞𝑛𝑒𝑡 = 𝑄𝑛𝑒𝑡 𝑚 (kJ/kg)
• Adiabatic system is a system with NO heat transfer: Q = 0

Three modes of heat transfer

• Conduction
• Convection
• Radiation

20
2.2.3.1 Conduction
Conduction – exchange of energy between stationary
molecules of a substance.

 dT
• Fourier’s law of heat conduction: Qcond   A k t
dx
𝑄𝑐𝑜𝑛𝑑 = heat flow per unit time (W; 1W=1J/s), i.e. dQ/dt
kt = thermal conductivity (W/mK)
A = area normal to heat flow (m2)
𝑑𝑇
= temperature gradient in the direction of heat flow (C/m)
𝑑𝑥

Exercise 2-1
A flat wall is composed of 20 cm of brick having a thermal conductivity kt =
0.72 W/mK. The right face temperature of the brick is 900C, and the left
face temperature of the brick is 20C. Determine the rate of heat
conduction through the wall per unit area of wall.

[ans: 3168 W/m2]

21
2.2.3.2 Convection
Convection - mode of energy transfer between a solid
surface and the adjacent liquid or gas that is in motion.

The rate of heat transfer by convection (𝑄𝑐𝑜𝑛𝑣 ) is

determined from Newton's law of cooling,
expressed as

Q conv  h A (Ts  Tf )

Energy is first transferred to the air

layer adjacent to the surface of the
𝑄𝑐𝑜𝑛𝑣 = heat transfer rate (W) block by conduction. This energy is
A = heat transfer area (m2) then carried away from the surface by
h = convective heat transfer coefficient (W/m2K) convection.
Ts = surface temperature (K)
Tf = bulk fluid temperature away from the surface (K)

22
2.2.3.2 Convection
Q conv  h A (Ts  Tf )
𝑄𝑐𝑜𝑛𝑣 = heat transfer rate (W)
A = heat transfer area (m2)
h = convective heat transfer coefficient (W/m2K)
Ts = surface temperature (K)
Tf = bulk fluid temperature away from the surface (K)
Note: in the absence of fluid
The convective heat transfer coefficient is an motion the heat is transferred
experimentally determined parameter that conducted by natural
convection.
depends upon the surface geometry, fluid
properties, nature of flow, and the bulk fluid
velocity. Ranges of the convective heat transfer
coefficient are:
h W/m2K
free convection of gases 2-25
free convection of liquids 50-100
forced convection of gases 25-250
forced convection of liquids 50-20,000
23
convection in boiling and condensation 2500-100,000
2.2.3.3 Radiation
Radiation – energy transfer from the surface of one body to
the surface of another due to electromagnetic radiation.
• The radiative energy transferred is proportional to the
difference in the fourth power of the absolute
temperatures of the bodies exchanging energy.


Q rad   A Ts4  Tsurr
4


Q rad = heat transfer per unit time (W)

A = surface area for heat transfer (m2)
σ = Stefan-Boltzmann constant, 5.67x10-8 W/m2K4 and 0.1713x10-8 BTU/h ft2 R4
 = emissivity
Ts = absolute temperature of surface (K)
Tsurr = absolute temperature of surroundings (K)

24
2.2 Energy transfer by work & heat

Similarities between work & heat

1. They are both boundary phenomena.

2. Both are associated with a process, not a

state. Unlike properties, heat or work has
no meaning at a state.

3. Both are path functions (i.e. their

magnitudes depends on the path followed
during a process as well as the end states).

25