Engr. Rolie A.

Castro

Deals with the study of the interrelation of

various forms of energy in a system.
Physical science concerned with the transfer
of heat and appearance/disappearance of
work.

1.

2.

To predict whether or not a particular

chemical process can take place under any
given condition.
To determine the amount of energy that
must be put into the process and its
maximum yield.

1.

2.

It does not involved calculation of the rates

of chemical reaction or physical processes,
which depends on both driving force and
resistance.
It does not reveal the molecular mechanism
of physical or chemical processes.

1.

System
a. Open (Control volume) w/ mass and energy
transfer
b. Closed (Control mass) energy transfer only
c. Isolated no mass and energy transfer
Closed
System
Mass Flow

dm

dt

Open
System
Mass Flow

Example: Piston and cylinder - a closed system

m

Piston
Gas at pressure, p

Example: The gas turbine engine - an open system

Fuel Flow In
Combustor

Air Flow In

Shaft Work Output

Compressor Work Out

Exhaust Gases Out

Surroundings

2.

3.

Region outside the system

Boundary

Region
separating
the
system
and
the
surroundings
a. Diathermic thermally conducting boundary
b. Adiabatic thermally insulating boundary

Universe = Systems +Surroundings

Surroundings

Closed System
System Boundary

Control Surface

Surroundings
Mass flow

Open System
( Fixed

space or
volume)

Open systems have mass flow across

their boundaries.

4.

Equilibrium State
a. State in which properties does not vary with time.
b. System is uniform (No iternalk T, P, Concn,
velocity gradient)
c. Net of heat flow, mass or work between system
and surrounding is zero.
d. Net rate of chemical reaction is zero.
Kinds of Equilibrium
4.1 Mechanical equilibrium equal pressure
4.2 Thermal equilibrium Equal temperature

5.

6.

Contact

a. Mechanical Contact change in pressure in

surroundings results to a change in pressure of
the system
b. Thermal Contact change in temperature of
surroundings results to a change in temperature
of the system

Property

a. Extensive dependent on the amount of matter

present (e.g. mass, volume, etc.)
b. Intensive independent on the amount of matter
present (e.g. density, temp, pressure, MW, etc.)

7.

Thermodynamic Functions
a. State functions variables that do not depend on
the path undertaken from initial to final state.
(e.g. H, U, T, P, A, G, etc.)
b. Path function variables dependent on path
undertaken from initial to final state
(e.g. Q, W, etc.)

7.

Thermodynamic Functions
a. State functions variables that do not depend on
the path undertaken from initial to final state.
(e.g. H, U, T, P, A, G, etc.)
b. Path function variables dependent on path
undertaken from initial to final state
(e.g. Q, W, etc.)

Two Types of Problems

1. Equilibrium Problems involve in
identification and prediction of equilibrium
state (e.g. Solution thermodynamics)
2. Energy flow Problems that involve
computation of work or the flow of heat,
either closed or open system)

s2

F d s 12 KE m g s 2 s1

12 KE 12 PE

p p gas p ambient
V2

We

V1

pdV
x2

dV Adx

We pAdx
x1

A gas is confined in a 0.47m diameter cylinder by a

piston, on which rests a weight. The mass of the piston
and weight together is 150 kg. The local acceleration of
gravity is 9.813 m/s2, and atmospheric pressure is
101.57 kPa.
(a) What is the force, in Newton, exerted on the gas by
the atmosphere, the piston, and the weight, assuming
no friction between the piston and cylinder?
(b) What is the pressure of the gas in kPa?
(c) If the gas in the cylinder is heated, it expands,
pushing the piston and weight upward. If the piston and
weight are raised 0.83 m, what is the work done by the
gas in kJ? What is the change in potential energy of the
piston and weight?

The variation of fluid pressure with height is

described by the differential equation:

Here, is specific density and g is the local

acceleration of gravity. Assume the system is an
ideal gas. Modeling the atmosphere as an
isothermal column of ideal gas at 283.15 K (1OC),
estimate the ambient pressure in Denver, where z =
1(mi1e) relative to sea level. For air, take M = 29
g/mol and R=8.314 J/mole-K

Formulated by Ralph Howard Fowler

Principle: If body A is in thermal equilibrium
with B, and body B is in thermal equilibrium
with C, then Body A is in thermal equilibrium
with Body C.

Two systems in thermal

equilibrium with a third
system are in thermal
equilibrium with each
other.

One kilogram of air is heated reversibly at

constant pressure from an initial state of 300 K
and 1 bar until its volume triples. Calculate W,
Q, U, and H for the process. Assume for air
that P V/ T = 83.14 bar-cm3/mol-K and Cp =
29 J/mol-K .

A sample consisting of 2.00 mol He is

expanded isothermally at 22C from 22.8 dm3
to 31.7 dm3
(a) reversibly,
(b) against a constant external pressure equal
to the final pressure of the gas, and
(c) freely (against zero external pressure).
For the three processes calculate q, w, U,
and H.

The constant-pressure heat capacity of a

sample of a 1 mole perfect gas was found to
vary with temperature according to the
expression Cp/(J K1) = 20.17+0.0.3665(T/K).
Calculate Q, W, U, and H when the
temperature is raised from 25C to 200C
(a) at constant pressure,
(b) at constant volume.

A sample of carbon dioxide of mass 2.45 g at

27.0C is allowed to expand reversibly and
adiabatically from 500 cm3 to 3.00 dm3. What is
the work done by the gas?

A piston-cylinder contains He gas initially at

150 kPa, 20oC and 0.5 m3. The Helium is now
compressed in a polytrophic process to 400 kPa
and 140oC. Determine the heat loss or gain
during the process.

Calculate the work (J) done by a sample of 0.10

mol Ne gas that expands isothermally from 0.6 L to
1.2 L at 0oC according to the following conditions:
a. against constant external pressure of 0.9 atm
b. against a variable pressure which varies with
volume according to the expression PVn=k and with
the given data

c.
d.

Px103 (atm)

194

134

100

79

V (L)

0.6

0.8

1.0

1.2

reversibly assuming ideal gas

reversibly assuming gas obeys Van der Waals
equation of state (a=0.86 Pa-m6/mol2 and
b=3.18x10-5 m3/mol)

Calculate the Joule-Thomson coefficient, JT

(K/MPa) of a chlorofluorocarbon (Cp = 0.6923
kJ/kg-K) using the following data at 25oC.
P (MPa)
H (kJ/kg)

0.02

0.06

0.10

0.14

0.18

0.22

0.26

287.5 286.7 285.9 284.9 284.3 283.4 282.8

Determine the maximum temperature when

ethane (Hcomb = 1,560,688 J/mole) is burned
with 25% excess air. Assuming the combustion
goes to completion.
The following constants may be used:
Product

CO2

5.457

1.045x10-3

-1.157x105

H2O

3.470

1.450x10-3

0.121x105

O2

3.639

0.506x10-3

-0.227x105

N2

3.280

0.593x10-3

0.640x105

A boiler is fired with high grade fuel oil (consisting

only of hydrocarbons) having a standard heat of
combustion of -43,515 J/g at 25oC with CO2(g) and H2O(l)
as products. The temperature of the fuel and air
entering the combustion chamber is 25oC. The air is
assumed dry. The flue gas leaves at 300oC, and their
average analysis (on dry basis) is 11.2% CO 2, 0.4% CO,
6.2% O2, and 82.2% N2. Calculate the fraction of the heat
of combustion of the oil that is transferred as heat to
the boiler.
Given also is the Cp/R of products at combustion
temperature:
Product
Cp/R

CO2

5.2352

CO

3.6005

H2O

4.1725

O2

3.7267

N2

3.5618

A lump of copper having mass of 10 lbm at a

temperature of 1000oF is dropped into a wellinsulated bucket containing 100 lbm of water at
a temperature of 70oF. If the specific heats of
copper and water are 0.095 and 1.000,
respectively, calculate the resulting changes in
entropy of the water and copper, and calculate
the total entropy change resulting from the
process.

a. A kilogram of water at 273 K is brought

into contact with a heat reservoir at 373K. When
the liquid water has reached 373 K, what is the
entropy change of water? Of the heat reservoir?
What is Stotal?
b. If the water had been heated from 273 to
373K by first bringing it in contact with a
reservoir at 323K and then with a reservoir at
373K, what would have been Stotal?

If 2.0 mol of N2 and 3.0 mol Ar, initially at the

same temperature and pressure, are allowed to
mix by removing the partition keeping them
apart, what is the entropy change?

Refer to the following data for two moles of

nitrogen gas which obey the van der Waals
equation of state:
T1 = 250 K
Cv = 28 J/mol-K
V1 = 5 L
a = 0.1408 Pa-m6/mol2
T2 = 100 K
b = 3.913 x 10-5 m3/mol
a. What is the change in internal energy (kJ)
accompanying the reversible expansion of this
gas to a final volume of 80L?
b. If the expansion was adiabatic and reversible,
what is the final volume (L) of the gas?