University of Mines and Technology

Chemical Process Calculations II

( RP 272)
CHAPTER 2
Benjamin Edem Meteku, PhD
Department of Chemical & Petrochemical Engineering
bemeteku@[Link]
July 2024
ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)

Chapter Two

ENERGY BALANCES ON CLOSED SYSTEMS

(UNSTEADY STATE)
ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
LEARNING OUTCOMES:
At the end of the chapter two every student should be able:
❖ Write the first law of thermodynamics (the energy
balance equation) for a closed process system.
❖ State the conditions under which each of the five terms in
the balance can be neglected.
❖ Given a description of a closed process system, simplify
the energy balance and solve it for whichever term is not
specified in the process description
ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Introduction:
❖ A system is termed open or closed based on whether mass
crosses the system boundary during the period of time covered by
the energy balance.
❖ A batch process system is by definition a closed system whiles a
semi-batch and continuous process systems are open.

❖ The Accumulation term equals the final value of the

balanced quantity (in this case, the system energy) minus the
initial value of this quantity.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Introduction:
❖ For Unsteady State System, one or more properties within
the system change(s) with respect to time.
❖ The General Balance Equation is:
Input –Output +Generation –Consumption =Accumulation
❖ Writing the general balance equation in terms of Energy,
we have the first law of Thermodynamics which states:
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Introduction:
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Introduction:
❖ However, since energy cannot be created or destroyed, it
implies that the following terms in the general equation:
1. Generation = 0
2. Consumption = 0
❖ Hence,
Accumulation = Input - Output
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Introduction:
Accumulation = Input – Output
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Introduction:
❖ Also, since the equation is written in terms of energy,
Input – Output = ∆ Energy (i.e K.E. + P.E. + U)
❖ For a closed system (such as a batch reactor), although
material cannot cross the system boundary, energy can be
transferred (cross the boundary) as heat (Q) and work (W)
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Equation and Terms:
❖ For a closed unsteady-state system, the energy balance is
given as;

……(2.1)
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Equation and Terms:
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Equation and Terms:
❖ If several components are involved in the process, then;
❖ Uinside is the sum of the mass (or moles) of each component, i,
times the respective specific internal energy of each component
i, Ûi.
❖ (Q +W) represents the total flow of energy into the closed
system.
❖ We do not put a Δ symbol (change in states) before Q or W
because they are not state variables.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Equation and Terms:
❖ Remember that Q and W are both positive when the net transfer
is into the system, and E represents the sum of (U + KE + PE)
associated with mass inside the system itself.
❖ Be careful; in some books W is defined as positive when done by
the system.
❖ Also keep in mind that each term in the Eqn represents the
respective net cumulative amount of energy over the time
interval from t1 to t2, not the respective energy per unit time, a
rate, which would be denoted by an overlay dot.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Example
1. If 250 J is added to a system as heat, what is the value of Q
in the energy balance equation?
2. If 250 J of work is done on the system, what is the value of
W in the energy balance equation.
3. If a closed system has an internal energy of 100 kcal at the
beginning of a process and 50 kcal at the end of the
process, what is ∆U?
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Answers
1. Q = 250 J
2. W = 250 J ( But for those using ∆E = Q – W,
W = -250J)
3. ∆U = - 50 J
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Equation and Terms:
NB
❖ In closed systems, the values of ΔPE and ΔKE in ΔE
are usually negligible or zero;
❖ Hence, often you see ΔU = Q + W used as the energy
balance because
- when the system is not accelerating, K.E. = 0
- when system is not rising or falling vertically, P.E. = 0
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples of Unsteady-State Closed Systems
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Equation and Terms:
NB
❖ For adiabatic processes or perfectly insulated systems, or if
a systems and its surroundings are at the same temperature,
Q=0
❖ If there are no moving parts or electrical currents or
radiation at the system boundary, then W = 0.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples of Unsteady-State Closed Systems

In the Figure 10 kJ of heat are

transferred through the fixed boundary
(bottom) of a vessel with 2 kJ being
transferred out at the top during the
same time period. Thus, ΔU = ΔE
increases by 8 kJ.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples of Unsteady-State Closed Systems

In Figure b, a piston does 5 kJ

of work on a gas whose internal
energy increases by 5 kJ.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples of Unsteady-State Closed Systems

In Figure c, the voltage

difference between the system
and surroundings forces a
current into a system to do a
work of 7 kJ. However, no
heat transfer occurs because
of the insulation on the system.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples of Unsteady-State Closed Systems
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.1)
Alkaloids are chemical compounds containing nitrogen that can be produced
by plant cells. In an experiment, an insulated closed vessel 1.673 m3 in volume
was injected with a dilute water solution containing two alkaloids: ajmalicine
and serpentine. The temperature of the solution was 10°C. To obtain an essentially
dry residue of alkaloids, all of the water in the vessel was vaporized.
Assume that the properties of water can be used in lieu of the properties of
the solution. How much heat had to be transferred to the vessel if 1 kg of
saturated liquid water initially at 10°C was completely vaporized to a final
condition of 100°C and 1 atm? See Figure E2.1. Ignore any air present in the
vessel (or assume an initial vacuum existed).
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.1)

Figure E2.1 Values from steam table

 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.1)
Solution:
• The system is the closed vessel; hence from the viewpoint of
the material balance it is steady-state, but from the viewpoint
of the energy balance it is unsteady-state.
• Sufficient data are given in the problem statement to fix the
initial state and the final state of the water. Using the
properties of water in the steam tables as provided. Note that
the specific volume of steam at 100°C and 1 atm is 1.673
m3/kg.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.1)
Solution:

For a closed system at unsteady-state, equation (2.1) applies:

ΔE = ΔU + ΔPE + ΔKE = Q + W
But
ΔPE = 0 (negligible)
ΔKE = 0 ( system not moving)
W = 0 ( No expansion or compression, no current or radiation)
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.1)
Solution:
Basis: 1kg of H2O evaporated
ΔE = ΔU + 0 + 0 = Q + 0
(we obtained values for specific internal Energy from table)
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.2)
A gas is contained in a cylinder fitted with a movable piston. The initial gas
temperature is 25°C. The cylinder is placed in boiling water with the piston held
in a fixed position. Heat in the amount of 2.00 kcal is transferred to the gas,
which equilibrates at 100°C (and a higher pressure). The piston is then
released, and the gas does 100 J of work in moving the piston to its new
equilibrium position. The final gas temperature is 100°C. Write the energy
balance equation for each of the two stages of this process and in each case
solve for the unknown energy term in the equation. In solving this problem,
consider the gas in the cylinder to be the system, neglect the change in
potential energy of the gas as the piston moves vertically, and assume the gas
behaves ideally. Express all energies in joules
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.2)
Solution: Stage 1
Since we have a closed system in an unsteady-state, equ.(2.1) applies:
Δ𝑈 + ΔKE + ΔPE = 𝑄 + 𝑊
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.2)
Solution: Stage 2
Since we have a closed system in an unsteady-state, equ.(2.1) applies:
Δ𝑈 + ΔKE + ΔPE = 𝑄 + 𝑊

But
ΔKE = 0 (the system is stationary at the initial and final states)
ΔPE = 0 ( Assumed negligible by hypothesis)
∆U = 0 ( U depends on only T for ideal gas and T does not ∆)
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.2)
Solution: Stage 2
0=𝑄+𝑊

The gas does a work of 100J on expansion (pushing the piston)

So W = (-) 100 J
0 = Q + (-100 J)
Q = 100 J
Thus, an additional 100 J of heat is transferred to the gas as it expands
and re- equilibrates at 100°C.
ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
General Strategy for Solving Energy Balance Problems
1. Choose the system, identify its boundary, and then decide whether
the system is open or closed. Write the decision down. Change it if
your first decision proves to be a poor one.
2. Decide if the system is steady state or unsteady state. Write the
decision down.
3. Write down the general energy balance, Equation (2.1) , for the
system.
4. Simplify the general energy balance as much as possible by using
information in the problem statement and reasonable assumptions
based on your understanding of the process.
ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
General Strategy for Solving Energy Balance Problems
5. Carry out a degree-of-freedom analysis that includes the energy
balance as one equation (that may include more than one additional
variable) along with the material balances and state your basis
6. Choose a reference state for your calculations, usually the
specification of temperature and pressure, but other variables may be
substituted.
7. Based on the reference state, get any needed physical property data
(T, p, and add the values of the data to the sketch of the process.
8. Solve the energy balance alone or in conjunction with the material
balances.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.3) Plasma Etching Application
Argon gas in an insulated plasma deposition chamber with a
volume of 2 L is to be heated by an electric resistance heater.
Initially the gas, which can be treated as an ideal gas, is at 1.5
Pa and 300 K. The 1000-ohm heater draws current at 40 V
for 5 min (i.e., 480 J of work is done on the system by the
surroundings). What are the final gas temperature and
pressure in the chamber? The mass of the heater is 12 g and
its heat capacity is 0.35 J/(g)(K). Assume that the heat transfer
through the walls of the chamber from the gas at this low
pressure and in the short time period involved is negligible.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.3) - Solution
Pick the system shown in Figure E2.1. No reaction occurs. The
fact that the electric coil is used to “heat” (raise the temperature of)
the argon inside the system does not mean that heat transfer takes
place to the selected system from the surroundings. Only work is
done. The system does not exchange mass with the surroundings;
hence it is steady-state with regard to mass but is unsteady state
with respect to energy.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.3)
Solution:
Steps 1– 4: Because of the assumption about the heat transfer from
the chamber wall, Q = 0.
W is given as + 480 J (work done on the system) in 5 min.
Step 5: Basis : 5 minutes
Steps 6-7:
The general energy balance (with ΔPE = ΔKE = 0 inside
the system) is
ΔE = ΔU = Q + W
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.3)
Solution:
Substituting values
∆U = 0 + 480 J
From the assumption in question, the gas is ideal hence
PV = nRT
But we initially know P, V and T so we can calculate amount of gas (n)
ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.3)
Solution:
Also, from the question,
mass of heater = 12 g and
heat capacity of the heater = Cv = 0.35 J/ (g)(K)
For the argon gas (which is an ideal gas as assumed in question)
Cv = Cp - R
Cp = (5/2)R (ie monoatomic gas such as argon)
So, we can find the Cv of the gas in terms of R
Cv = (5/2)R –R
Cv of the argon gas is (3/2)R where R = 8.314 Pa.m3
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.3)
Solution:
You have to pick a reference temperature for the calculations.
The most convenient reference state is 300 K (from Question). Then
ΔU for the gas and the heater can be calculated assuming both the
heater and the gas end up at the same temperature:
The obtained ∆U = 480 J (is for both the heater and the argon gas)
For the Gas:
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.3)
Solution:
For the Heater:

Step 8:
We calculate for T from the energy balance equation
∆U = ∆Uheater + ∆Ugas
Hence
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.3)
Solution:

T = 414 K
Now, to calculate for final pressure:
P1V1 = n1RT1 ……(1)
P2V2 = n2RT2 ……(2)
Equation (2) / (1)
But n1 is the same as n2
ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.3)
Solution:
T1 = 300 K T2 =414 K
P1 = 1.5 Pa P2 = ?
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.4)
A tank with the volume of 5 m3 contains 0.05 m3 of
saturated liquid water and 4.95 m3 of saturated steam. Heat is
transferred to the tank until the tank is filled with saturated
steam only. Calculate the heat transfer of this process
[values from steam table provided]
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.4)
Solution: Stage 1
Since we have a closed system in an unsteady-state, equ.(2.1) applies:
Δ𝑈 + ΔKE + ΔPE = 𝑄 + 𝑊

But
ΔKE = 0 (the system is stationary at the initial and final states)
ΔPE = 0 ( No vertical displacement)
W = 0 ( No expansion or compression – ie boundaries not changing)
Δ𝑈 = 𝑄
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.4)
Solution: Stage 1

Q =∆U = U2 – U1
Referring from steam tables at P = 0.1 MPa,
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.4)
Solution: Stage 1
Assessing the quality of the steam by looking at the dryness
fraction (x) at state 1
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.4)
Solution: Stage 1
Solving for the specific internal energy at state 1 ( u1)
( specific internal energy at the gaseous state and liquid state)

Internal energy U1 = mass x specific internal energy

 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.4)
Solution: Stage 1

x ( 542.68)
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.4)
Solution: Stage 2
We determine the specific volume of the gaseous state

Now, we need to find a point in the saturated steam table with a

specific volume of 0.098. Referring to the steam table, we identify that
there is no point with vg = 0.098.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.4)
Solution: Stage 2
We determine the specific volume of the gaseous state

Now, we need to find a point in the saturated steam table with a

specific volume of 0.098. Referring to the steam table, we identify that
there is no point with vg = 0.098.
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.4)
Solution: Stage 2
We can only determine the specific internal energy at this point by
interpolation from steam tables.
vg =0.1044 ug = 2599.4 and vg =0.0862 ug = 2602.4
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.5)
A 2 kg mass of water is initially at 25°C in a well-insulated
container. A heating element inside the container is turned on
and supplies 500 W of power to the water. Determine the
temperature of the water after 10 minutes. Assume no heat is
lost to the surroundings and that the specific heat capacity of
water is 4.18 kJ/(kg·°C).
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.5)
Solution:
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.5)
Solution: 2
Energy Balance for Closed System
∆U = Q + W
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.5)
Solution:
 ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)
Examples (Q 2.5)
Solution:
300kJ = 2 kg x 4.18 kJ/(kg.℃) x ∆T
∆T = 35.89 ℃
ENERGY BALANCES ON CLOSED SYSTEMS (UNSTEADY STATE)

Chapter Two

ENERGY BALANCES ON CLOSED SYSTEMS

(UNSTEADY STATE)