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ChE 122 Lecture notes 03 (2.7 to 2.10 of syllabus)

FIRST LAW IN CLOSED/NON-FLOW SYSTEMS,
ENTHALPY, HEAT CAPACITY, FIRST LAW IN
OPEN/STEADY-FLOW SYSTEMS

First Law of Thermodynamics

applied in a closed/non-flow system
General mathematical statement of 1st law:
Euniverse = constant
Euniverse = 0
Esystem + Esurroundings = 0
For non-flow closed system:
Esystem = (U + PE + KE)system
Since closed system, no energy associated with
matter is transported through the boundary,
therefore all energy changes are in terms of heat
and work such that:
Esurroundings = +/- Q +/- W
But in our calculations, Q and W always refer to
the system (basis for sign convention), taking the
positive signs:
Esystem = Q + W
(U + PE + KE)system = Q + W
However for non-flow, closed system they often
undergo processes that cause no change in
external energies (PE and KE) but only change in
internal energy U. So the equation can reduced
to:
U = Q + W

Note: derived for non-flow, closed

system! Also, this is a simplification for systems with
negligible PE and KE changes.

In differential form:
d(nU) = dQ + dW
where n is the total mol of homogeneous fluid
under consideration for the closed system
Recall the equation of W for closed,non-flow
system also:
W = -PdV

Substituting:
d(nU) = dQ Pd(nV)
Note: This is the
general energy balance equation for n mol of
homogeneous fluid in a closed, non-flow
system undergoing a mechanically, reversible
process (thats why in differential form).
--------------------------------------------------------------------------------Exercises:
1. An egg, initially at rest is dropped onto a
concrete surface and breaks. With the egg
treated as the system:
a. Determine the type of thermodynamic system.
b. What is the sign of W?
c. What is the sign of PE?
d. What is the sign of KE?
e. What is U?
f. What is the sign of Q?
In modeling this process, assume the passage of
sufficient time for the broken egg to return to its
initial temperature. What is the origin of the heat
transfer in part (f)?
2. Water flows over a waterfall 100m in height.
Take 1 kg of the water as the system and assume
that it does not exchange energy with its
surroundings.
a. Type of thermodynamic system
b. What is the potential energy of the water at
the top of the falls with respect to the base of the
falls?
c. What is the kinetic energy of the water just
before it strikes bottom?
d. After the 1 kg of water enters the stream below
the falls, what change has occured in its state?
3. A gas is confined in a cylinder by a piston. The
initial pressure of the gas is 7 bar and the volume
is 0.10m3. The piston is held in place by latches in
the cylinder wall. The whole apparatus is placed
in a total vacuum. What is the energy change of
the apparatus if the restraining latches are
removed so that the gas suddenly expands to
double its initial volume, the piston striking other
latches at the end of the process?

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If the process is repeated not in a vacuum but in
air at atmospheric pressure of 101.3 kPa, what is
the energy change of the apparatus? Assume the
rate of heat exchange between the apparatus
and the surrounding air is slow compared with the
rate at which the process occurs.
-------------------------------------------------------------------------------SPECIAL CASES : CONSTANT V OR
CONSTANT P (STILL AT CLOSED, NON-FLOW SYSTEMS)
A. CONSTANT VOLUME
If the process occurs at constant total volume ,
the non-flow work is zero. (why do you think?)
d(nU) = dQ
Q = nU (constant V, but why is the
integral of U a change in U vs Q?)
Thus the heat transferred in a mechanically
reversible, constant volume, closed system
process is equal to the internal energy change of
the system.
B. CONSTANT PRESSURE
d(nU) = dQ Pd(nV)
dQ = d(nU) + Pd(nV)
If constant pressure, finite:
Q = nU + PnV
Defining U + PV = H (enthalpy):
dQ = d(nH) (if differential)
At integration:
Q = nH
(constant P)
The heat transferred in a mechanically
reversible, constant pressure, closed
system process is equal to the enthalpy change
of the system.

dH = d(U) + d(PV)
H = U + PV
--------------------------------------------------------------------------------Exercises :
1. Calculate the change in U and H for 1 kg of
water when it is vaporized at the constant
temperature of 100 deg C and the constant P of
101.33 kPa. The specific volumes of liquid and
vapor water at these conditions are 0.00104 and
1.673m3/kg. For this change, heat in the amount
of 2,256.9 kJ is added to the water. However
before doing the calculations, identify the type of
thermodynamic system involved.
2. A nonconducting container filled with 25 kg of
water at 20 deg C is fitted with a stirrer which is
made to turn by gravity acting on a weight of
mass 35 kg. The weight falls slowly through a
distance of 5m in driving the stirrer. Assuming
that all work done on the weight is transferred to
the water and that the local acceleration of
gravity is 9.8m/s2, determine:
a. the type of thermodynamic system
b. the amount of work done on the water
c. the internal energy change of the water
d. The final temperature of water if Cp is 4.18 kJ/
(kg-K)
e. The amount of heat that must be removed
from the water to return it to its initial
temperature
f. the total energy change of the universe
because of (1) the process of lowering the weight,
(2) the process of cooling the water back to its
initial temperature and (3) both process together.
--------------------------------------------------------------------------------HEAT CAPACITY, C
- amount of heat required to raise the
temperature of an object or substance one
degree.
The smaller the temperature change in a body
caused by the transfer of a given quantity of
heat, the greater is its capacity.

ENTHALPY

Question:

Because U,P and V are state functions, H is also a

state function. In differential form:

1. If heat cannot be stored (because it only exists

in transit like work), why do we have the concept
of heat capacity?

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2. Which has a greater heat capacity: metals or
water?
Heat capacity, C = dQ/dT (in differential form,
e.g. unit - J/K)
However, this makes C a process dependent
function rather than a state function. It suggests
the definition of 2 quantities that are state
functions.
A. CONSTANT VOLUME
C = (dQ/dT)
At constant volume: Cv = (dU)/(dT)
dU = Cv dT
T2

At integration:

U =

Cv dT
T1

Combining previous constant volume process:

T2

Q = nH = n

Cp dT
T1

This is applicable for a mechanically reversible,

constant pressure process!
Special note:H, Cp and T are state functions. So
only the initial and final state matters in the
calculation whether the process happens in
actual constant pressure process or whether P
changes but returns to initial value.
Note also that work here is not necessarily zero.
--------------------------------------------------------------------------------ANNOUNCED QUIZ ON APPLICATION OF
FIRST LAW TO CLOSED/NON-FLOW
SYSTEMS!!!
---------------------------------------------------------------------------------

T2

Q = nU = n

Cv dT
T1

This is applicable for a mechanically reversible,

constant volume process!
Special note: If volume varies during the
process but returns to its initial state such that
change in V is zero and V1 is same as V2, the
process cannot be rightly called constant volume.
However notice that Cv, U and T are state
functions therefore one can use: U =

Cv dT

A. MEASURES OF FLOW

B. CONSTANT PRESSURE
C = (dQ/dT)
At constant pressure: Cp = (dH)/(dT)
dH = Cp dT
T2

At integration:

First Law of Thermodynamics

applied in open/steady-flow systems

H =

Cp dT
T1

The following are the common measures of flow:

Mass flow rate,

Molar flow rate,

Volumetric flow rate, q

Velocity, u
Relevant equations
(1) Continuity equation:

Combining previous constant pressure process:

m 1=m 2

This form of the continuity equation is applicable

only for steady-state system where there is but a
single entrance and a single exit stream.

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(2) Law of conservation of mass material
balance!

>> A piston illustration demonstrating these

works for closed vs open system shall be
discussed in class for better visuals <<
--------------------------------------------------------------------------------Exercises:
1. Liquid n-hexane flows at a rate of 0.75 kg/s in a
pipe with inside diameter 5cm. Assuming that the
density is 659 kg/m3, determine the volumetric
flow rate, molar flow rate and velocity. Also for a
pipe diameter of 2 cm.

pq=density x volumetric flow rate

(3) m=
(4)

q=uA=velocity x area

(5) Mass flux, G = pu =

density x velocity

B. ENERGY BALANCE
Consider a steady-state, steady flow, open
system:

Ws
PE1
KE1
U1
WFLOW1

Control Volume

PE2
Q

KE2
U2
WFLOW2
EIN = EOUT
PE1 + KE1 + U1 + WFLOW1 +Q + Ws = PE2 + KE2 + U2
+ WFLOW2
Q + Ws = (PE2-PE1) + (KE2-KE1) + (U2-U1) + (W2W1)FLOW
Q + Ws = PE +KE+ (U + PV)
Q + Ws = PE +KE+ H
of Van Ness)

(See Eqn 2.32a

Nuancing WORK
Shaft work = work done on or by the process fluid
by/on a moving part in the system. A better term
for this is external work any work that is not
flow work for open systems.
Flow work = work that is necessary to maintain
continuous flow of mass in and out of system

2. On a circular conduit there are different

diameters: diameter D1 = 2m changes into D2 = 3
m. The velocity in the entrance profile was
measured: u = 3 m/s. Calculate
the discharge and mean velocity at the outlet
profile.
3. Air at 1 bar and 25 deg C enters a compressor
at low velocity, discharges at 3 bar and enters a
nozzle in which it expands to a final velocity of
600m/s at the initial conditions of pressure and
temperature. If the work of compression is 240 kJ
per kilogram of air, how much heat must be
removed during compression? What do you think
is included as component of our system?
4. Water at 93.5 deg C is pumped from a storage
tank at the rate of 3.15 x 10-3 m3/s. The motor for
the pump supplies work at the rate of 1.5 kW. The
water goes through a heat exchanger giving up
heat at the rate of 700 kW and is delivered to a
second storage tank at an elevation 15m above
the first tank. What is the temperature of the
water delivered to the second tank? What do you
think is included as component of our system?
--------------------------------------------------------------------------------ANNOUNCED QUIZ ON APPLICATION OF
FIRST LAW TO OPEN/STEADY FLOW SYSTEM
--------------------------------------------------------------------------------PROBLEM SET FOR LECTURE 1 TO 3
--------------------------------------------------------------------------------FIRST LONG EXAM!