Engi-3434

Chemical Engineering Thermodynamics

Dr. Charles Xu @ Chemical Engineering, Lakehead University

Chapter 2 The First Law of Thermodynamics

Example 2.7
Calculate the internal-energy and enthalpy changes that occur when air is changed from an initial state of 4(C) and 10(atm), where its molar volume is 0.002278m3(g mole )-1, to a final state of 60(C) and 1 (atm). Assume for air that P V / T is constant and that Cv= 20.93 and CP= 29.31J(g mole)1(C)-1.
Solution: Take 1 g-mol air contained in an imaginary piston/cylinder as the system:
Because changes in properties (state functions) U and H are independent of the path. We can assume two reversible steps in which 1 (g mole) of air is (a) cooled at constant volume to the final pressure, and (b) heated at constant pressure to the final temperature.

P a

P1, V1, T1

b
P, V, T

P2, V2, T2

V
T1 = 4 + 273.15 = 277.15 K T2 = 60 + 273.15 = 333.15 K Since PV/T = Const, the final volume (V2) is
P1V1 P2V2 (10atm)(0.002278m 3 ) (1atm)V2 = = V2 = 0.0274m 3 T1 T2 277.15 K 333.15K

Solution to Example 2.7 (contd)

(a) The first step: cooling at const V = V1 = 0.002278 m3 until the final pressure (P2=1 atm) is reached. The temperature at the end of this step is thus

P1V1 P'V1 (10atm)(0.002278m 3 ) (1atm)(0.002278m 3 ) = = T ' = 27.715 K T1 T' 277.15K T'

Q =nU = nCVT = (1 g-mol)(20.93J/mol/K)(27.715K-277.15K) = 5220.7J H = U + (PV) = U + (P)(V) = 5220.7J + (1101325Pa 10101325Pa)(0.002278m3) = 7298J

(b) The second step: heating at const P = P2 = 1 atm, until the final volume V2=0.0274 m3 and temperature T2 = 333.15K is reached.

Q = nH = nC P T = (1 g - mol)(29.31

J )(333.15 K 27.715 K ) = 8952.3 J mol K

U = H - (PV) = H - PV = 8952.3J (1.0101325Pa)(0.0274m3 0.002278 m3) = 6406.8J For the entire process (2 steps): U = (5220.7J) + (6406.8J) = 1186.1J H = (7298J) + (8952.3J) = 1654.3J

2.12 Mass and Heat Balance for Open System

Measures of Flow
Mass Flowrate: Molar Flowrate:
Cold media in

& m (kg/s) & n (mol/s)

& m (kg/s)

Volumetric Flowrate: Velocity:

q (m 3 /s)
Cold media out

u (m/s)

Relations between Measures of Flow

& & m= M n
where M is molar mass (kg/mol)

& m = q = uA where A is the cross-sectional area (m2) and is specific density (kg/m3)

q = uA

& n = q = uA where A is the cross-sectional area (m2) and is molar density (mol/m3)

2.12 Mass and Heat Balance for Open System (Contd) Mass Balance for Open Systems
Consider a control volume (CV) with flow streams (fs), the mass balance can be written as

dmCV & + (m) fs = 0 dt

or

denotes as out in (2.26)

dmCV & + (m) fs = 0 dt

dmCV + ( uA) fs = 0 dt dmCV = 0 , thus dt

Continuity equation of the system

At steady state,

& (m) fs = ( uA) fs = 0

When there is but a single entrance and a single exit,

& m = Const = 1u1 A1 = 2 u 2 A2

u A u A & m = Const = 1 1 = 2 2 V1 V2

or

where V is specific volume (m3/kg): V=1/

2.12 Mass and Heat Balance for Open System (Contd)

General Energy Balance for Open Systems

Consider a control volume (CV) with flow streams (fs), the energy balance is
d (mU ) cv 1 1 & & & = (U + u 2 + zg )m (U + u 2 + zg )m + Q + ( work rate) dt 2 2 fs ,in fs ,out

where U is the specific internal energy (J/kg), m is the mass the control volume. The work associate with the CV may include several forms: the PV work to move the flowing streams through entrance and exits, other types of work W (such as shaft work Ws, stirring work, expansion and contraction of the CV, etc.). Thus & & & +W ( work rate) = [( PV )m] [( PV )m]
fs ,in fs ,out

The energy balance is now:

d ( mU ) cv 1 1 & & & & & & = (U + u 2 + zg )m (U + u 2 + zg ) m + Q + [( PV )m] fs ,in [( PV )m] fs ,out + W dt 2 2 fs ,in fs ,out 1 1 & & & & + Q +W = (U + PV + u 2 + zg ) m (U + PV + u 2 + zg )m 2 2 fs ,in fs ,out

2.12 Mass and Heat Balance for Open System (Contd)

General Energy Balance for Open Systems

d (mU ) cv 1 1 & & & & = Q +W (U + PV + u 2 + zg )m + (U + PV + u 2 + zg )m dt 2 2 fs ,in fs ,out

Note that H = U + PV and denote as out in

d (mU ) cv 1 & & & + ( H + u 2 + zg )m = Q + W dt 2 fs

(2.28)

For some applications, kinetic- and potential-energy changes in the flowing streams are negligible, i.e., 1 2 & ( u + zg )m 0 2 fs The energy balance equation (2.28) is simplified to

d (mU ) cv & & & + (Hm ) fs = Q + W dt

(2.29)

Example 2.8
Show the first law of thermodynamics for a close system can be derived from the general heat balance equation (2.29). Solution:

Example 2.9
An insulated, electrically heated tank for hot water contains 190 kg of liquid water at 60C when a power outage occurs. If a stream of cold water at 10C flows in and a withdrawn stream flows 1 & out the tank at a constant rate of m = 0.2kgs . How long will it take for the temperature of the water in the tank to drop from 60 to 35C? Assume negligible heat losses from the tank and for liquid water, Cv = CP = C, independent of T and P, and assume a perfect mixing of the tank water.

Solution:

2.12 Mass and Heat Balance for Open System (Contd)

Energy Balance for Steady-State Flow Systems

d (mU ) cv =0 For steady-state systems, the accumulation term in Eq. (2.28) . In dt such system the mass within the control volume is constant, and no changes occur with time in the properties within the whole system, and the work W = Ws

1 & & & ( H + u 2 + zg )m = Q + Ws 2 fs

(2.30)

& When there is but one entrance and one exit, m

1 & & & & & mH + m u 2 + mzg = Q + Ws 2
Or,

= Const
(2.31)

The energy balance equation (2.30) is simplified to

H +

& & u 2 Q W + gz = + s & & m m 2

H +

u 2 + gz = Q + Ws 2

(2.32)

All terms in (2.32) are in units of J/kg-fluid

Example 2.10
Air at 1 bar and 25C enters a compressor at low velocity, discharges at 3 bar, and enters a well-insulated nozzle in which it expands to a final velocity of 600 ms-1 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? Solution (To be given at tutorial #3):