Chapter 18:

Heat, Work, and the First Law of Thermodynamics

 The first law of thermodynamics and how

it extends the principle of conservation of
energy to thermal phenomena
 To understand the work and heat involved
in basic thermodynamic processes:
• Isothermal
• Constant volume
• Isobaric
• Adiabatic
 To understand how molecular structure
determines the specific heat of an ideal
gas
 The 1st law of thermodynamics
 Two ways to raise temperature

Thermally: flow of heat from Mechanically: doing work, 𝑊𝑊

temperature difference, 𝑄𝑄

End result is the same for the same energy input:

An increase in the system’s internal energy, ∆𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 (𝑜𝑜𝑜𝑜 ∆𝑈𝑈)
 The 1st law of thermodynamics
 Extended version of “conservation of energy” by including
thermal processes
 The change in the internal energy of a system depends
only on the net heat transferred to the system and the net
work done on the system, independent of the particular
processes involved.
Change in The heat The work
internal energy = added + done
of a system to the system on the system

∆𝑈𝑈(or ∆𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 ) = 𝑄𝑄 + 𝑊𝑊 Text book formula

If the work is done

∆𝑈𝑈(or ∆𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 ) = 𝑄𝑄 − 𝑊𝑊 by the system
 Reversible and irreversible processes (가역, 비가역)

When changing the state of a system,

 In a reversible process
• The system remains always in thermodynamic equilibrium
and follows a path in its p-V diagram
• Any process carried out slowly enough to be quasi-static
(no abrupt change of T) is reversible.
• It is possible to reverse the system’s path in its p-V diagram.

 In an irreversible process
• The system goes temporarily out of
equilibrium without well-defined values
for T, P, and other quantities
• Although the system has no well-defined
Different points in
path in the pV diagram, it ends up in the pV diagram
represent different
a definite state, back in equilibrium. states of the system.
 Doing Work
 A piston-cylinder system is a useful device for describing the
thermodynamic behavior of a gas.
• The piston seals the cylinder, allowing the gas volume to change
without any gas escaping.
• Work can be done on or by the gas as the piston moves.
• If the bottom is uninsulated, heat can flow in or out.
 The work done on the gas is the negative of the area under the pV
curve:
From ∆Eint = Q + W and
𝐹𝐹∆𝑥𝑥 = 𝑝𝑝𝑝𝑝∆𝑥𝑥 = 𝑝𝑝∆𝑉𝑉
W = −p∆V (negative area),
the internal energy is
∆Eint = Q −p∆V.
 Doing Work
 A piston-cylinder system is a useful device for describing the
thermodynamic behavior of a gas.
• The piston seals the cylinder, allowing the gas volume to change
without any gas escaping.
• Work can be done on or by the gas as the piston moves.
• If the bottom is uninsulated, heat can flow in or out.
 The work done by the gas is the positive of the area under the pV
curve:
From ∆Eint = Q − W and
W = +p∆V (positive area),
the internal energy is
∆Eint = Q −p∆V.
 Got It?
 Two identical gas-cylinder systems are taken from the same
initial state to the same final state, but by different processes.
Which of the following is or are the same in both cases?
(a) the work done on or by the gas
(b) the heat added or removed
(c) the change in internal energy

 Thermodynamic state variables: a quantity whose value doesn’t depend on

how a system got into its particular state.
e.g.: pressure, volume, temperature, internal energy, thermal entropy

 Heat and work are not thermodynamic state variables. They are process
functions.
 Isothermal Process and the Ideal Gas
(등온)

 An isothermal process takes place at constant

temperature (T = constant) .
• One way to achieve this is to keep the system
in thermal contact with a heat reservoir.
(reservoir = a much larger system held at constant T)
• The ideal gas law gives P = nRT/V.
• With constant T, the work done on the gas is

• The temperature and internal energy do not

change, ΔEint = Q + W = 0.

Heat must be transferred from outside to the system, when

the system does work without a change in temperature.
 Constant-Volume Process
(등적)
 In a constant-volume process (also called isometric, isochoric, or
isovolumic, V = constant), the heat added to the gas and the resulting
temperature change are related by
Q = nCV ∆T
where CV = molar specific heat at constant volume (J/K·mol)

 No work is done in a constant-volume process,

so W = 0 and the first law reads ∆Eint = Q.
• Therefore ∆Eint = Q = nCV ∆T.
• For an ideal gas, internal energy depends on temperature alone.
• So the relationship ∆Eint = nCV ∆T between ∆Eint and ∆T holds for
any process.

The temperature change is converted into the internal

energy change, because of no work.
 Isobaric Process
(등압)

 An isobaric process takes place at constant pressure (P = constant) .

Then the work done (on the gas) is W = –p ∆V.
 Adding heat to an ideal gas results both in a temperature change and
in work being done. ∆Eint = nCV ∆T = Q + W.
• Therefore it takes more heat to
effect a given temperature change:

• The molar specific heat at

constant pressure, Cp, expresses
this extra work (using pΔV = nRΔT):

• Thus
  Isometric vs isobaric process

 Isometric : ∆V = 0, Q = nCV ∆T = ∆Eint

Heat goes to raise the internal energy, i.e., temperature only.

 Isobaric : ∆P = 0, Q = nCP ∆T = nCV ∆T + nR ∆T = n(CV + R)∆T

Heat is used for the mechanical work and to raise temperature.
 Adiabatic Process
(단열)

 In an adiabatic process, no heat flows into or out of the system.

• Therefore Q = 0 and the first law reads ∆Eint = W.
• Analysis of the adiabatic process for an ideal gas shows that

where is the ratio of specific heats of the gas.

• An adiabatic curve or adiabat is steeper than an isotherm
because the gas does work.
It therefore loses internal energy and its temperature drops.
• In terms of temperature, we have

• The work done is

p2V2 − p1V1
W= (from problem 69)
γ −1
Derivation of

 Q = 0, ∆Eint = nCV ∆T = W = –p∆V

 From pV = nRT, p∆V + V∆p = nR∆T
 nCV ∆T/nR∆T = CV /R = –p∆V/(p∆V + V∆p)
 CV V∆p + CV p∆V = –Rp∆V
CV V∆p + (CV +R)p∆V = 0
CV V∆p + CP p∆V = 0
dp/p + (CP /CV) dV/V = 0, after integrating
ln p + (CP /CV) ln V = 0, using CP /CV = γ
ln p + γ ln V = 0
ln pVγ = 0
 Therefore,
pVγ = constant, TVγ-1 = constant
 Deriving adiabatic equation 18.12

From pV γ = constant , p1V1γ = pV γ

p1V1γ
p= γ
V

p2V2 − p1V1
W=
γ −1
Ideal-Gas Processes: a Comparison

𝑝𝑝𝑝𝑝 = 𝑛𝑛𝑛𝑛𝑇𝑇 ∆𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑄𝑄 + 𝑊𝑊

 Cyclic Processes
 Thermodynamic processes with a complete cycle
(back to its starting state)
• Important in technological systems like engines and refrigerator.
• The work done on or by the gas in a cyclic process is
the area enclosed by the process curve in the pV diagram.
 Example 18.4: Work in cyclic process
For pA=100 kPa, VA= 4 L, and γ = 1.4,
using the relation, pVγ = constant,
we get pB= 696.4 kPa and VB= 1 L.

 WA→B (adiabatic, Q = 0) = (pBVB – pAVA)/(γ –1)

= (696.4 x 1 – 100 x 4)/(1.4 – 1) = 741 J
 WB→C (isometric, V = constant) = 0
 From PV = nRT = constant,
WC→A (isothermal, T = 300 K = constant) = – nRT ln (VA/VC) = – 555 J
 Net work = 741 J + 0 – 555 J = 186 J

Note:
1. No internal energy change, returning to the initial state.
2. Positive net work on counterclockwise cycling path because we have done net
work on the gas. The work done on it is transferred to its surrounding as heat.
3. Only heat transfer occurs along the path B→C, no heat flow on A→B,
and heat absorption on C→A.
 Optional
p-V diagram for the ideal Diesel and Otto cycle
 Otto cycle is used by gasoline ignition
whereas diesel engine uses the diesel cycle.

Isentropic process: adiabatic + reversible

From Wikipedia
 Work done by cyclic process of diesel engine

The work done (by the system) and heat absorbed during each of the four processes

1 → 2 (adiabatic) W12 =( p1V1 − p2V2 )/(γ − 1), Q12 =0

2 → 3 (isobaric) W23= p2 (V3 − V2 ), Q23= nCP (T3 − T2 ) ≡ Qh
3 → 4 (adiabatic) W34 =( p3V3 − p4V4 )/(γ − 1), Q34 =0
4 → 1 (isovolumic) =
W41 0,=
Q41 nCV (T1 − T4 ) ≡ −Qc

For the whole cycle, the work done

p1V1 − p2V2 + p3V3 − p4V4 γ ( p3V3 − p2V2 ) − p4V4 + p1V1
=W = + p3V3 − p2V2
(γ − 1) (γ − 1)
 Specific Heats of an Ideal Gas
 The specific heat of an ideal gas depends on its molecular structure.
• More complex molecules have more degrees of freedom, or ways they can
absorb energy.
• Monatomic gases (He, Ne, Ar): 3 degrees of freedom per molecule
(three directions of translational motion (vx, vy, vz))
3 3
𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑛𝑛𝑛𝑛𝑛𝑛, ∆𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑛𝑛𝐶𝐶𝑉𝑉 ∆𝑇𝑇 = 𝑛𝑛𝑛𝑛∆𝑇𝑇,
2 2
3
we get 𝐶𝐶𝑉𝑉 = 𝑅𝑅.
2
In addition, the adiabatic exponent is
𝐶𝐶 𝐶𝐶𝑉𝑉 +𝑅𝑅 5
𝛾𝛾 = 𝑃𝑃 = = = 1.67
𝐶𝐶 𝑉𝑉 𝐶𝐶𝑉𝑉 3
• Diatomic gases (H2, O2, N2): 5 degrees of freedom
per molecule (three translational and two rotational)
5 5
𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑛𝑛𝑛𝑛𝑛𝑛, 𝐶𝐶𝑉𝑉 = 𝑅𝑅
2 2
The adiabatic exponent is
𝐶𝐶𝑃𝑃 𝐶𝐶𝑉𝑉 +𝑅𝑅 7
A diatomic molecule
𝛾𝛾 = 𝐶𝐶𝑉𝑉
=
𝐶𝐶𝑉𝑉
= = 1.4
5
has rotational as well as
translational energy.
 Equipartition Theorem
 Equipartition theorem:
When a system is in thermodynamic equilibrium, the average energy
1
per molecule is 𝑘𝑘𝑘𝑘 for each degree of freedom.
2
• For three translational directions, (vx, vy, vz),
3 1 1 1 3 3
𝑢𝑢 = 𝑘𝑘𝑘𝑘 = 𝑘𝑘𝑘𝑘 + 𝑘𝑘𝑘𝑘 + 𝑘𝑘𝑘𝑘, 𝑈𝑈 = 𝑛𝑛𝑁𝑁𝐴𝐴 𝑘𝑘𝑘𝑘 = 𝑛𝑛𝑛𝑛𝑛𝑛
2 2 2 2 2 2
• At moderately high temperature, a triatomic molecule such as NO2 can
have 6 degrees of freedom per molecule (3 translational and 3 rotational),
and has a volume specific heat CV = 3R, and γ = 4/3 = 1.33.

(Example 18.5)
For a gas mixture (2 mole of O2 and 1 mole of Ar)

5 5
O2: ∆𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑘𝑘𝑘𝑘 𝑛𝑛𝑁𝑁𝐴𝐴 = 𝑛𝑛𝑛𝑛𝑇𝑇 = 5𝑅𝑅𝑅𝑅
2 2
3 3 3
Ar: ∆𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑘𝑘𝑘𝑘 𝑛𝑛𝑁𝑁𝐴𝐴 = 𝑛𝑛𝑛𝑛𝑛𝑛 = 𝑅𝑅𝑅𝑅
2 2 2
1 𝑑𝑑𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 1 3 13
NO2 CV = 𝑑𝑑𝑑𝑑 = 5 + 𝑅𝑅 = R
𝑛𝑛 3 2 6
 Quantum Effects
 In Newtonian physics, rotational and vibrational energies can be arbitrarily
small.
 In contrast, quantum physics sets minimum limits on rotational and
vibrational energies for a given molecule.
 At normal temperatures there may not be enough thermal energy to excite
any vibrational mode (or certain rotational modes).
• For instance, at room temperature a diatomic molecule has only five
degrees of freedom (3 translational and 2 rotational) since there is not
enough thermal energy to cause it to vibrate or rotate about its long axis.
 Chapter 18 Summary
 The first law of thermodynamics: the change in a system’s internal
energy is equal to the heat added to the system minus the work done by
the system: ∆Eint = Q – W
 Thermodynamic processes take systems between states in their pV
diagrams. Reversible vs irreversible processes
 Important ideal-gas processes

 Cyclic process: combine the thermodynamic processes to take a system

through a complete cycle
 The specific heats of an ideal gas depend on the structure of the gas
molecules.