NPS 210 – Physics for Engineers

THE LAWS OF THERMODYNAMICS

Thermodynamics = the study of processes in which energy is transferred as heat and as work

system = is any object or set of objects that we wish to consider

closed system = is one for which no mass enters or leaves (but energy may be exchanged with the environment)
the system.

open system = is one for which mass may either enter or leave (as well as energy) the system.

thermodynamic system = a system that can interact (and exchange energy) with its surroundings or environment in at
least two ways, one of which is heat transfer

thermodynamic equilibrium = when a system is in the state of mechanical, thermal, and chemical equilibrium

mechanical equilibrium : “There is no unbalanced force acting in the interior of the system or between the
system and its environment.”
thermal equilibrium: “All parts of the system are at the same temperature, and it is the same as the temperature
of the environment.”
chemical equilibrium: “ The net rate of chemical reaction or change of internal structure is zero.”

When a system is in thermodynamic equilibrium, its condition can easily be specified by giving values of only few
quantities called variables of state, namely: pressure (P), volume (V), temperature (T), and quantity of a particular
substance (n).

When heat is added to a system, there is an increase in the internal energy of the system.

Internal energy (U) = is a property of a system that is equal to the sum of the kinetic energies of all its constituent particles
plus the sum of all potential energies of the interaction among these particles.

Manifestations of increase in internal energy:

1. rise in temperature
2. increase in pressure
3. change in phase

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U = nRT
2 for monatomic ideal gas

The change in internal energy (U) of the system is the difference in its internal energy in the initial and final
states. That is:
ΔU =U 2−U 1 where U = final internal energy and U = initial internal energy
2 1

If the internal energy of the substance changes and if at the same time the substance is allowed to perform
external mechanical work, the heat required will be:

Q= ΔU +W Equation of the First Law of Thermodynamics

Statement: “When heat is transformed into any other forms of energy or when other forms of energy are
converted into heat, the total amount of energy is constant.”

Meaning: “When Q is added to a system, some of this added energy remains within the system, changing its U by
an amount U, the remainder leaves the system again as it does W against its surroundings.”

 The First Law of Thermodynamics is a generalization of the principle of conservation of energy.

Sign conventions for Q and W:

Q is + when it flows into the system.
Q is – when it flows out of the system.
W is + when it is done by the system against its surroundings.
W is – when it is done on the system by its surroundings.
Note:
W and Q are not properties of a system hence; they are dependent on the initial and final states and .on
the path (intermediate state) taken by the system. U is dependent on the initial and final states of the system but not on
the path taken by it.

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Equations of Sate = equations that we can use to express the relationship among the variables of state

Examples:
V =V o [ 1+ β ( T −T o )−k ( P−Po ) ] for solid or liquid material

mtot = nM for total mass ( M = molecular/molar mass)

PV =nRT Ideal gas equation ( R = 8.3145 J/mol  K , universal gas constant)

mtot
In terms of total mass: PV = RT
M
PM
In terms of density: ρ=
RT

P1V1 = P2V2 Boyle’s Law

T 1 T2
= Charles’ Law
V1 V2

P 1 P2
= Gay Lussac’s Law
T1 T 2

P1V 1 P2V 2
= Combined Gas Law
T1 T2

Heat capacities of gases

cp = specific heat capacity at constant pressure

cv = specific heat capacity at constant volume

R
c p −c v=
M

For monatomic gases: (Gases that are composed of only one atom like helium (He), argon (Ar), xenon (Xe),
radon (Rn) , etc.)
5R 3R
c p= cv =
2M and 2M

For diatomic gases: (Gases that are composed of two atoms like hydrogen (H2), oxygen (O2), nitrogen (N2),
carbon monoxide(CO) , etc.)
7R 5R
c p= cv =
2M and 2M

cp Cp
=γ =
cv Cv for monatomic gases:  = 1.67 and for diatomic gases:  = 1.40

In terms of molar heat capacities:

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C v = R = 12.47 J/mol  K for ideal gas of point particles
2

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C v = R = 20.79 J/mol  K for diatomic gases
2

C v =3 R for an ideal monatomic solid

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C p=C v + R= R for an ideal monatomic gas
2

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C v= R for an ideal diatomic gas
2

THERMODYNAMIC PROCESSES: (are processes in which there are changes in the state of a thermodynamic system)

1. Isothermal = is carried out at constant temperature

When a system of mass m expands isothermally against a pressure P, the internal energy does not change.
U = 0 and Q = W
If the system is an ideal gas: PV = nRT
Using Boyle’s Law and Ideal Gas Law, the heat added or the work done is calculated using:
V2 V2
Q=W =P1 V 1 log e Q=W =2 .303 P1 V 1 log
V1 or V1

V2 P1
Q=W =P1 V 1 ln Q=W =P1 V 1 ln
V1 or P2

P1 V2
Q=W =nRT ln Q=W =nRT ln
P2 V1

PV diagram for an ideal gas undergoing isothermal processes at two different temperatures:
P

a a

b higher T isotherm = the curve for isothermal process

b
lower T
V

2. Adiabatic = is one in which no heat is allowed to flow into or out of the system
Q = 0 and U = -W

The situation can occur if the system is extremely well insulated, or the process happens so quickly that
heat – which flows slowly – has no time to flow in or out.

P

adiabat = the curve for adiabatic process (steeper than isotherm)

isothermal


adiabatic
V

The Boyle’s Law and Charles’ Law for ideal gases (under adiabatic process):
P1 V γ =P2 V T 1V =T 2 V γ −1
1 2γ and 1γ −1 2

Work done adiabatically:

W =nC v ΔT or
W =mc v ΔT
or
Cv 1
γ−1 ( 1 1 2 2 )
W= ( P1 V 1 −P2 V 2 ) W= P V −P V
R or

3. Isobaric = is one in which the pressure is kept constant

When a system of gas mass m is heated at constant pressure P,

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 Q= ΔU +W or
Q=mc p ΔT

U = mcvT and W = m(cp – cv)T

Also;
W = PV or W = Fd
W = P(V2 – V1) W = PAd

4. Isochoric or Isovolumic = is one in which the volume does not change

When a system of gas of mass m is heated at constant volume,
W = 0 and Q = U or Q = mcvT

P isobaric
a b
a

isochoric
b
V

5. Cyclic process – a process that eventually returns a system to its initial state

U2 = U1 so ΔU = 0 Q=W

 For any process taking place in an isolated system,

U2 = U1 = ΔU = 0 Q = W= 0

Sample Problems:

1. A 25.0-L tank contains 0.280 kg of helium at 24C. The atomic mass of helium is 4.00 g/mol. A) How many moles of are
in the tank? b) What is the pressure in the tank in pascals and in atmospheres?

2. A room with dimensions 5.00 m x 6.00m x 3.00 m is filled with pure oxygen at 22.0 C and 1.00 atm. The molecular mass
of oxygen is 32.0 g/mol. a) How many moles of oxygen are required? b) What is the mass of this oxygen in kilograms?

3. Helium gas with a volume of 1.90 L, under a pressure of 2.5 atm and at a temperature of 53.0 C is warmed until both
pressure and volume are doubled. a) What is the final temperature? b) How many grams of helium are there?
The atomic mass of helium is 4.00 g/mol.

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4. a) An amount of heat equal to 2500 J is added to a system and 1800 J of work is done on the system. What is
the change in internal energy of the system?
b) What would be the internal energy change if 2500 J of heat is added to the system and 1800 J of work is done
by the system?

5. In an engine, 0.2 mole of gas in the cylinder expands rapidly and adiabatically against the piston. In the process, the
temperature drops from 1150 K to 400 K. How much work does the gas do? Assume the gas is ideal.

6. Determine the change in internal energy of 1.0 L of water at 100 C when it is fully boiled which results in 1671 L of
steam at 100 C. Assume the process is done at atmospheric pressure.

7. Two moles of an ideal gas are compressed slowly and isothermally from a volume of 4.0 to 1.0 ft3 at a temperature of
300 K. How much work is done?

8. In each case, find the change in internal energy of the system.

a. A system absorbs 2000 J of heat at the same time does 600 J of external work.
b. A system absorbs 1250 J of energy at the same time 425 J of work are done on it.
c. From a gas held at constant volume, 4 kJ of heat is removed.

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9. Compute for cv, cp, and  for nitrogen gas. Molar mass is 48.0 g/mol.

10. The temperature of 4 kg of nitrogen gas is raised from 20 C to 140 C. a) If this is accomplished at constant
pressure, find the external work done by the gas. B) Find the heat required to accomplish this at constant volume.
For N2, cv = 741 J/kgK and cp = 1040 J/kgK.

11. How much work is done by a gas in expanding from an initial volume of 3.5 liters at 2.0 x 105 Pa to a final volume
of 25 liters, the temperature remaining constant?

12. A series of thermodynamic processes is shown in a PV diagram below. In process ab, 150 J of heat are added to the
system and in the process bd, 700 J of heat are added. Find: a) the change in internal energy in process ab, b) the
change in internal energy in process abd, and c) the total heat added in process acd.

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 P

P2 b d P1 = 2 x 104 Pa
P2 = 8 x 104 Pa
P1 a c V1 = 2.0 x 10-3 m3
V2 = 4.0 x 10-3 m3
NPS 210 – Physics for Engineers V
V1
SECOND LAW OF THERMODYNAMICS V2

 Thermodynamic processes that occur in nature are all irreversible.

 Reversible processes are equilibrium processes, with the system always in thermodynamic equilibrium.
 A reversible process is an idealization that can never be precisely attained in the real world. But by making the
temperature gradients and the pressure differences in the substance very small, the system can be kept very close to
equilibrium states and make the processes nearly reversible.

Statements:
1. Heat flows naturally from a hot object to a cold object; heat will not flow spontaneously from a cold object to a hot
object. (R.J.E. Clausius) – called the “refrigerator” statement

heat engine = is any device that changes thermal energy into mechanical work, such as steam
engines and automobile engines (gasoline engines and diesel engines)

efficiency of heat engine = the ratio of the work done by the engine to heat input (QH)

W
e=
QH where QH = W + QC or W = QH – QC where QC =output heat at low temperature
or

QC TC
e=1− e ideal =1−
Q H and TH where TC & TH are the operating temperatures

2. No device is possible whose sole effect is to transform a given amount of heat completely into work. (Kelvin-
Planck) – called the “engine” statement

There can be no perfect heat engine. There can be no perfect refrigerator.

For refrigerators and air conditioners, the coefficient of performance (CP):

QC QC TC
K= K= K ideal =
W or
Q H −QC and
T H −T C

heat pump = device that can heat the house in winter by taking heat QC from the outside of the house, by
doing work W

QH
K=
For heat pumps: W

3. The total entropy of any system plus that of its environment increases as a result of any natural process.

Meaning: Natural processes tend to move toward a state of greater disorder.

Entropy (S) = is a quantitative measure of the disorder of a system

= stays the same in idealized (reversible) process, S = 0, or increases in any real process, S > 0.

 If the system is not isolated, then the change in entropy of the system, Ss, plus the change in entropy of
the environment, Senv, must be greater than or equal to zero;
S = Ss + Senv  0.

The change in entropy of a system, when an amount of heat Q is added to it by a reversible process at
constant temperature (isothermal process), is given by;

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 Q
ΔS =
T where T is in Kelvin ( absolute temperature).

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In an infinitesimal reversible process: ∆ S=∫ dQ
T
where 1 & 2 are the initial and final states.
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For mixtures:
QH QC
ΔS H = ΔS C =
ΔS =ΔS H + ΔS C where T ave and
T ave

Sample Problems:
1. A heat pump has a coefficient of performance of 3.0 and is rated to do work at 1500 W. a) How much heat can it
add to a room per second? b) If the heat pump were turned around to act as an air conditioner in the summer,
what would you expect its coefficient of performance be, assuming all else stays the same?

2. A gasoline truck engine takes in 10,000 J of heat and delivers 2000 J of mechanical work per cycle. The heat is
obtained by burning gasoline with heat of combustion Lc = 5.0 x 104 J/g. (a) What is the thermal efficiency of this
engine? (b) How much heat is discarded in each cycle? (c) If the engine goes through 25 cycles per second, what is
its power output in watts? In horsepower? (d) How much gasoline is burned in each cycle? (e) How much gasoline
is
burned per second? Per hour?

3. An ice cube of mass 60 g is taken from a storage compartment at 0 C and placed in a paper cup. After few
minutes, exactly half of the mass of the ice cube has melted, becoming water at 0 C. Find the change in entropy of
the ice/water.

4. A sample of 50.0 kg of water at 20 C is mixed with 50 kg of water at 42 C. Estimate the change in entropy.

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5. An automobile engine has an efficiency of 20% and produces an average of 23000 J of mechanical work per second
during operation. How much heat is discharged from this engine per second?

6. A steam engine operates between 500 C and 270 C. What is the maximum possible efficiency of this engine?

7. A heat engine produces 8200 J of heat while performing 3200 J of useful work. What is the efficiency of this
engine?

8. If an ideal refrigerator keeps its contents at –15 C when the house temperature is 22 C, what is its coefficient of
performance?

9. What is the change in entropy of 100 g of steam at 100 C when it is condensed to water at 100 C?

10. One kilogram of water is heated from 0 C to 100 C. Estimate the change in entropy of the water.

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13. An ideal gas is slowly compressed at a constant pressure of 2.0 atm (1 atm = 1.0 x 105 Pa) from 10.0 L to 2.0 L. This
process is shown in the figure below as the path B to D. (In this process, some heat flows out and the temperature
drops.) Heat is then added to the gas, holding the volume constant and the pressure and temperature are allowed
to rise until the temperature reaches its original value. The process is D to A. Calculate a) the total work done by
the gas in the process BDA, and b) the total heat flow into the gas.

Pa A

Pb D B
V
Va Vb

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