CH-214

CHEMICAL ENGINEERING THERMODYNAMICS-I

CHAPTER 2
THE FIRST LAW AND OTHER
BASIC CONCEPTS
Adnan Akhtar
Adnan.Akhtar@sharif.edu.pk
 JOULE’S EXPERIMENT
 Amount of work done and temperature is measured
Joule showed that
For each fluid a fixed amount of work per unit
mass was required for each degree of
temperature rise caused by the stirring
The original temperature of the fluid was
restored by the transfer of heat through simple
contact with a cooler object.
 These experiments demonstrated the existence of a
quantitative relationship between work and heat,
and thereby showed that heat is a form of energy
CLASSIFICATION OF ENERGY
 In Joule’s experiments, energy added to a fluid as work is later transferred from the fluid
as heat.

Where does this energy reside after

its addition to, and before its
transfer from, the fluid?
 Kinetic (motion) energy and Potential (position) energy – external macroscopic energies
 Another form of energy – cause by internal molecular rotational, vibrational and
translational motions

 Internal Energy
INTERNAL ENERGY
 Energy due to motion of molecules relative to the center of mass of the system, to
the rotational and vibrational motion of the electromagnetic interactions of the
molecules is known as to be internal energy (U).

 Energy of the molecules internal to the substance

 Addition of heat increases molecular activity – Increase U
 Extensive Property – as is the total energy
INTERNAL ENERGY
 The change in the total energy of a system is
E2-E1 = (U2-U1) + (KE2-KE1) + (PE2-PE1)

Or ΔE = ΔU + ΔKE + ΔPE

 There are no internal-energy meters, we can just calculate the change in U.

 Internal energy of the system changes, when there is a change in temperature,
change in phase, change in chemical structure, i.e. chemical reaction.
 THE FIRST LAW OF
THERMODYNAMICS
Although energy assumes many forms, the total quantity of energy is constant,
and when energy disappears in one form it appears simultaneously in other
forms.

 Heat and work represents energy in transit across the boundary dividing the system
from its surroundings and are never stored or contained in the system. Boundaries
can be real or imaginary, rigid or flexible.

 First law applies to the system and surroundings, not to the system alone.
∆(Energy of the system) + ∆(Energy of the surroundings) = 0
 ENERGY BALANCE FOR CLOSED
SYSTEMS
 No streams enter or leave a closed system, no energy associated with matter is transported across the
boundary
 All energy exchange between a closed system and its surroundings is in the form of heat or work, and the
total energy change of the surroundings equals the net energy transferred to or from it as heat and work
Δ(Energy of surroundings) = ±Q ± W

 Transfer of Heat, Energy and Work INTO the System Positive while in other case Negative
 The corresponding quantities taken with reference to the surroundings, Q surr and Wsurr, have the opposite
sign, i.e.,
Qsurr = −Q
Wsurr = −W
 ENERGY BALANCE FOR CLOSED
SYSTEMS
Δ(Energy of surroundings) = Qsurr + Wsurr = −Q − W
Δ(Energy of the system) = Q + W
This equation states that the total energy change of a closed system equals the net energy transferred into it
as heat and work.
Closed systems often undergo processes during which only the internal energy of the system changes:
∆Ut = Q + W
Differential form: dUt = dQ + dW
Although Ut for a homogeneous system of arbitrary size are extensive properties, specific and molar
internal energy U are intensive.
∆(nU) = n ∆U = Q + W
d(nU) = ndU = dQ + dW
Energy Balance for Closed Systems
 Q +ive -ive Q

Surrounding SYSTEM Surrounding

+ive -ive
W W

Work done BY the system on the surrounding: Negative (-ive)

Work done ON the system by its surrounding: Positive (+ive)
 THERMODYNAMIC STATE AND
STATE FUNCTIONS
 Thermodynamic properties reflect changes in the thermodynamic state.
Temperature, pressure and density are examples.

 For a homogeneous pure substance, fixing two of these properties also fixes all the
other, thus determines its thermodynamic state.

 For example nitrogen gas at a temperature of 300 K and a pressure of 105 kPa (1 bar)
has a fixed specific volume or density and a fixed internal energy. Hence it has a
complete set of independent (intensive) thermodynamic properties.

 The thermodynamic properties that do not depend on the past history of the
substance nor on the means by which it reaches a given state. They depend only on
present conditions, however reached. Such quantities are known as state function.
 THERMODYNAMIC STATE AND
STATE FUNCTIONS
 Difference in Quantity (Amount) and Property (Change)
 Differential of a state function represents an infinitesimal change in its value.

 The differentials of heat and work are not changes but an infinitesimal amounts.

When integrated, these differentials give not finite changes, but finite amounts.
 PRACTICE PROBLEM (EXAMPLE 2.4)
• When a system is taken from state a to state b in
the accompanying figure along path acb, 100 J of
heat flows into the system and the system does 40
J of work.

• (a) How much heat flows into the system along path
aeb if the work done by the system is 20 J?

• (b) The system returns from b to a along path bda. If the

work done on the system is 30 J, does the system
absorb or liberate heat? How much?
EQUILIBRIUM
 Equilibrium is a static condition, denoting absence of change and absence of any tendency towards change
with time.
 Static Conditions: No change in state of the system
• Mechanical Equilibrium (no pressure difference)
• Thermal Equilibrium (no temperature difference)
• Phase Equilibrium (no phase change)
 Resistance and Driving Forces: the capacity/capability of the system to disturb the equilibrium state of a
system
 Different kinds of forces tend to bring about different kinds of change. For example, change in pressure on
a piston causes energy transfer as work, temperature difference leads to heat transfer.
 Equilibrium in Chemical Reaction
PHASE RULE
 For homogeneous Pure Substance (e.g., an ideal gas), we need two intensive
properties to define its state (for example, T and p)

 When two phases are in equilibrium, the state of the system is fixed when
only a single property is specified

 For multiphase system, the number of independent variables that must be

arbitrarily fixed to establish its intensive state
PHASE RULE (DOF)
Gibbs phase rule was proposed by Josiah Willard Gibbs for non reactive multi component
heterogeneous systems in thermodynamic equilibrium
• F = 2-π + N

• Where
π = number of phase
N = number of chemical species
F = Degree of freedom
PHASE RULE (DOF)

 The phase rule gives the same information for a large system as for a small one and for different
relative amounts of the phases.
 The minimum number of degree of freedom for any system is zero. In which condition?

Triple point of water

F =2 – 3 + 1 = 0
 All three phases exist 0.01oC (273.15K) and 0.0061 bar.
 Any changes from these conditions can cause at least one phase to disappear.
PRACTICE (EXAMPLE 2.5)
• How many degrees of freedom has each of the following system?

a) Liquid water in equilibrium with its vapor? (F = 1)

b) Liquid water in equilibrium with a mixture of water vapor and nitrogen? (F = 2)
c) A liquid solution of alcohol in water in equilibrium with its vapor? (F = 2)
THE REVERSIBLE PROCESS
 A process is reversible when its direction can be reversed at any point by an
infinitesimal change in external conditions.
 Reversible Expansion of a Gas
 Reversible Chemical Reaction
 A reversible process
• is frictionless
• is never more than differentially removed from equilibrium
• traverses a succession of equilibrium state
• is driven by forces whose imbalance is differential in magnitude
• can be reversed at any point by a differential change in external conditions
• when reversed, retraces its forward path, and restores the initial state of system and
surroundings
THE REVERSIBLE PROCESS
 Reversible process should be carried out very slowly, or in other words such processes are carried out in very
small stages such that it can be reversed at any stage very easily.
 The process is therefore in equilibrium at all time. On the contrary irreversible processes are not in
equilibrium.

 Reversible process yields the maximum amount of work.

Work done (W) = Force x distance
W = (pressure x area) x distance
W = Pressure x (expanded volume)
W = Pexternal (Vfinal – Vinitial)
REVERSIBLE EXPANSION OF A GAS
• Assumptions:
• No heat loss and friction
• Low density and gravity-induced pressure gradient are very small relative
to its pressure
• Potential energy of the gases are negligible compared to the potential-
energy changes of the piston assembly.

 Dissipative Process (Irreversible) System

 Removal of small mass increment or mass in powder

form (Reversible)
REVERSIBLE CHEMICAL
REACTION
• Decomposition of calcium carbonate
 Frictionless and constant temperature bath piston-
cylinder contain CaCO3, CaO and CO2 in equilibrium
 The temperature is adjusted to a value such that the
decomposition pressure is just sufficient to balance the
weight on the piston (mechanical equilibrium)
 Chemical reaction held in equilibrium by CO2 pressure
 Any change of conditions, however slight, upsets the
equilibrium and causes the reaction to proceed in one
direction or another.
REVERSIBLE CHEMICAL REACTION
 If the weight is differentially increased, the CO2 pressure rises
differentially and CO2 combines with CaO to form CaCO3 allowing
the weight to fall slowly.
 The heat given off by this reaction raises the temperature in the
cylinder, and heat flows to the bath.
 Decreasing the temperature differentially sets off the opposite chain of
events.
 The same results are obtained if the temperature of the bath is
changed heat flows into the cylinder and calcium carbonate
decomposes.
 EXAMPLE 2.6 (J M SMITH)
A horizontal piston/cylinder arrangement is placed in a constant-
temperature bath.
The piston slides in the cylinder with negligible friction, and an external
force holds it in place against an initial gas pressure of 14 bar.
The initial gas volume is 0.03 m3.
The external force on the piston is reduced gradually, and the gas
expands isothermally as its volume doubles.
If the volume of the gas is related to its pressure so that the product PVt
is constant, what is the work done by the gas in moving the external
force?
CONSTANT-V AND CONSTANT-P
PROCESSES FOR CLOSE SYSTEMS
• Revision of studied basic formulas
Equation from Energy
Balance for Close
System
d (nU )  dQ  dW
Work for

dW   Pd (nV )
Mechanically
Reversible Process in
a close system

Energy Balance for

Mechanically Reversible
Process in a close d (nU )  dQ  Pd (nV )
system
Constant
Volume
Process
Constant
Pressure
Process
ENTHALPY
dQ = d(nU) + P d(nV)
dQ = d(nU) + d (nPV)
dQ = n d(U + PV)
• The appearance of U+PV term is the introduction to a new thermodynamic property and its mathematical
definition is
H = U + PV
dQ = d(nH)
Thus the heat transfer in a mechanically reversible, constant pressure, closed system process is equal to the
enthalpy change of a system.
The enthalpy plays a role in constant-pressure processes analogous to the internal energy in constant-
volume processes.
 CONSTANT-V AND CONSTANT-P PROCESSES
Constant Volume Process Constant Pressure Process
dQ  d (nU ) dQ  d (nU )  d (nPV )
Q  nU dQ  d  n(U  PV ) 
Internal Energy Change
H  U  PV
dQ  d (nH )
Q  nH
Enthalpy Change
 CONSTANT-V AND CONSTANT-P

The above equations Where as for mechanical

shows that in a reversible, constant
mechanically reversible,
pressure, closed system the
constant volume, closed
process equals the enthalpy
system process equals the
internal energy change of change of the system.
the system.
HEAT CAPACITY
The heat capacity is the amount of heat required to raise the temperature
of an object or substance by one degree. The temperature change is the
difference between the final (Tf) and initial temperature(Ti).
Mathematically C = dQ/dT
The above equation shows that the smaller the temperature change in a
body caused by heat transfer of a given quantity of heat, the greater is its
capacity.
 HEAT CAPACITIES ()
• Heat Capacity at constant • Heat Capacity at Constant
Volume Pressure
 U   H 
CV    CP   
 T V  T  P
dU  CV dT dH  CP dT
T2 T2
U   CV dT H   CP dT
T1 T1
T2 T2
Q  nU  n  CV dT Q  nH  n  CP dT
T1 T1