Chap.

2 The first law and other basic concepts

The first law is that energy is conserved.

2.4 Energy balance for closed system

No transfer of matter or mass is allowed between a system and its surrounding.

Heat and work cross the boundary.

∆U + ∆EK + ∆EP = Q + W
U is internal energy, EK is kinetic energy and EP is potential energy.
Q is heat and W is work. Q and W are regarded as positive when they are transferred into the
system from the surroundings.

Internal energy (U) = energy associated with all molecular, atomic, and subatomic motions
and interactions. It is difficult to determine absolute internal energy. What is important is the
difference in internal energy between states.
kinetic energy =  mu where m is the mass and u is the speed of the molecules in a system.

gravitational potential energy = mgh where g is the gravitational acceleration and h is the
elevation relative to the earth’s surface.

Closed systems often undergo processes during which only the internal energy (U) of the
system changes or ∆EK + ∆EP = 0.
Then,
∆U  Q  W in integral form, and
dU =dQ + dW in differential form.

(∆U)system + (∆U)surroundings = 0.

Internal energy (J) is an extensive property and molar internal energy (J/mol) is an intensive
property.

The mass of the system is constant, but the volume may not be constant. For a gaseous
system, the volume is variable unless the system boundary is rigidly fixed.

U is a state function, which is independent of the path by which it reaches a given state. In
comparison, Q and W are not state functions and they depend on the path.

(Example 2.1)

Flow work (Wf) = work required to push a material into the system at the inlet or out of the
system at the outlet.
Wf = Pv where P is the pressure and v is the volumetric flow rate.
Shaft work (Ws) = work to rotate the shaft connected to a system. (compressors and pumps

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for flow systems)
Work due to change in volume (Pressure-Volume work):
Work (W) = 
F • ds where F is the force and s is the displacement.
 

W= 
PA • ds  
P • As  
P • dV where P is the pressure. A is the

     

cross sectional area, and V is the volume.

By definition in the textbook, dW = -PextdV
Pext: external pressure or pressure outside the system

A work by isothermal expansion of gas in multiple steps is illustrated as follows:

The expansion above was carried out in four steps by removing the cubes on the piston one
by one. The rectangles with solid boundary lines under the P-V curve represent the amount of
work obtained by the expansion and those with the dotted lines represent the amount of work
required to return the gas to the initial condition. By increasing the number of the cubes while
maintaining the total mass of the cubes constant, the total area of the solid rectangles become
closer to that of the dotted rectangles, approaching the area under the P-V curve. With infinite
number of cubes or infinite number of steps, the work obtained by expansion is virtually the
2
same as that required to return the gas to the initial condition. This means that net work is
zero for the cycle of expansion and compression to indicate that it is a reversible process.

A reversible process is a process that can be returned to the initial condition by an

infinitesimal change in external condition.

For reversible expansion or compression, Pext = Psys

For a reaction of CaCO3 = CaO + CO2, there exists an equilibrium pressure at which CaCO3
and CaO coexist in equilibrium. If the CO2 pressure increases slightly higher the equilibrium
pressure, CaO combines with CO2 to form CaCO3. Decreasing the pressure slightly below the
equilibrium pressure reverse the reaction for CaCO3 to be converted into CaO. This is an
another example of reversible process.

Example 2.6

Example 2.7 (student)

Enthalpy (H) = U + PV where P is the pressure and V is the volume of a system. Enthalpy is
used preferentially in place of internal energy for energy balances for open systems at
constant pressure.

U=U(T,V), H=H(T,P)
Molar internal energy is a function of temperature and molar volume and molar enthalpy is a
function of temperature and pressure.

∂U ∂U
dU    dT    dV
∂T ∂V
∂H ∂H
dH   
   dP
∂T ∂P

By definition, C     and C
   

Cv; heat capacity at constant volume

Cp: heat capacity at constant pressure
Heat capacity: amount of heat necessary to raise the temperature of 1 kg of a substance by 1
degree, J kg-1 K-1

Cv and Cp are nearly the same for all solids and most of liquids, but differ considerably for
gases (Cp > Cv). Cp = Cv + R for ideal gases, where the units of Cp and Cv are J/(mol•K).
Cp and Cv are functions of temperature.

∂U
dU  C dT    dV
∂V
∂H
dH  C
dT    dP
∂P

at constant volume, dU = CVdT

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at constant pressure, dH = CP dT

∆H  Q at constant pressure.
∆U = Q at constant volume
The effects of molar volume on internal energy and of pressure on enthalpy are usually small
and neglected for simplicity in this chapter. The effects of volume and pressure will be
considered later in chapter 6.

Then,

dU  C dT
dH  C
dT

On integration,

∆U   C dT



∆H   C
dT


Example 4.2

∆U and ∆H associated with phase changes:

Heat of fusion (solid to liquid) = -heat of solidification (liquid to solid)

Heat of vaporization (liquid to vapor) = - heat of condensation (vapor to liquid)
Heat of sublimation (solid to vapor)

The Clapeyron equation:

4
 dP 
∆H  T∆V
dT
∆V is the volume change accompanying the phase change.

The latent heat of vaporization can be calculated from vapor-pressure and volumetric data.

Rough estimates of latent heats of vaporization for pure liquids at their normal boiling points:

 10 (Trouton’s rule)
∆


2.12 Energy balance for open systems,

An open system involves mass flow in the energy balance. If mass flows in and out of a
system, the mass carries energy (U, PE and KE) along with it.

∆E  Q  W  enegy input associated with mass )low in

+ energy output associated with mass )low out  )low work input
+ )low work output
Where ∆E is accumulation rate in energy in the system. It is zero at the steady state.

Energy input associated with mass flow in = (U1 + KE1 + PE1)m1 where U1, KE1, and PE1
are the internal energy, kinetic energy, and potential energy, respectively, that are put in the
system per unit mass, and m1 is the mass of flow in.

Energy input associated with mass flow out = (U2 + KE2 + PE2)m2 where U2, KE2, and PE2
are the internal energy, kinetic energy, and potential energy, respectively, that leave the
system per unit mass, and m2 is the mass of flow out.

Flow work input = p1V1m1 where p1 is the pressure and V1 is the specific volume at the inlet.

Flow work output = p2V2m2 where p2 is the pressure and V2 is the specific volume at the
outlet.

∆E  Q  W  .
 /0  10 m
+ .  /0  10 m  p
V
m
+ p V m

By rearranging,

∆E  Q  W  U
 p
V
 KE
 PE
 + U  p V  KE  PE 

 Q  W  H
 KE
 PE
 + H  KE  PE 
 Q  W + ∆H  KE  PE
This is equivalent to equation (2.28).

Example 2.13

Example 2.14

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At the steady-state for open systems
The accumulation term is zero.

Input (H + KE + PE) – output (H + KE + PE) + Q + Ws =0.

For constant level and small flow rate, KE and PE are neglected.
Assume there is no shaft work. Then, Input(H) – output(H) + Q =0.
or Q = ∆H

Steam Tables

Specific volumes and specific enthalpies of saturated and superheated steams at various
pressures

1) What is the temperature of the saturated steam at 50 psi?

2) What is the specific volume of the steam at 400 oF and 50 psi?
3) Determine the fraction of steam in a mixture of saturated steam and water at 50 psi
whose specific enthalpy is 500 Btu/lb?

Compare the values from the steam tables and those from the attached CD (Physical
Properties> CE PhyProp1.exe)

Standard Heat of Reaction

∆H,

: standard heat of formation for compound i
Heat of formation: enthalpy change associated with the formation of 1 mol of a compound
from its constituent elements as they normally occur in nature (e.g., O2 rather than O).

Standard condition: 1 atm and 25oC.

∆H : standard heat of reaction = ∑ υ ∆H,



Unit: J/mol (of extent of reaction)

For an instantaneous extent of reaction, ξ, the heat of reaction is calculated by ξ∆H .

How to determine heat of reaction at temperatures other than 25oC?

∆H T  ∆H 25 C  7  υ C
,

dT
.


How to calculate energy balance with chemical reaction?

Q  ∑ n H + ∑ n, H, =∆H

n  n,  υ ξ
Q  78n,  υ ξ:H + 7 n, H,  7 n, 8H + H, :  ξ 7 υ H

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By definition, ∆H  ∑ υ H

Q  7 n,  C
,

dT  ξ∆H
,

Q  7 n,  C
,

dT  ξ∆H 25 C  7  υ C
,

dT
, .


All species involved in the reaction are counted.

The right hand side is a function of T for a given ξ.

Q=0 (adiabatic): no heat transfer across the boundary or completely insulated.

The temperature at the outlet with Q=0 is called adiabatic temperature

For a problem where T (outlet temperature) is given, Q can be determined.

How much cooling is required for a specified outlet temperature?

For multiple reactions,

n  n,  7 υ, ξ

Q  7 n,  C
,

dT  7 ξ ∆H,

,

Q  7 n,  C
,

dT  7 ξ ∆H,

25 C   7 υ, C
,

dT
, .


Heating value: The negative of the standard heat of combustion for a fuel such coal or oil.
Higher (gross) heating value (HHV): heating value when the product water is liquid.
Lower (net) heating value (LHV): heating value when the product water is vapor.

Example 4.6

Example 4.7

Example 4.8

Example 4.9