CHEMICAL ENGINEERING THERMODYNAMICS Course no: CHE C311 / F213 Dr.

Srinivas Krishnaswamy 1st Semester 2012 2013 DEPT. OF CHEMICAL ENGG. BITS PILANI, K. K. BIRLA GOA CAMPUS

Contents
Reversibility and Irreversibility What is quasi-equilibrium? Understanding energy The concept of thermodynamic work Evaluation of work for common reversible processes Work done in an irreversible process Two inherently irreversible processes Heat and its comparison with work

Reversibility and Irreversibility

A process is reversible if it can be completely reversed, i.e. when carried out in the opposite direction the system follows the same succession of states as it followed in the forward direction (very crude definition) A process is reversible if after the process occurs, the system can be restored to its original state without any effect on its surroundings This effect occurs only when the driving force is infinitesimally small

Reversibility and Irreversibility

Note The 2nd definition involves the surroundings Important to understand that when a process is reversible, interaction between system and surroundings are equal and opposite in direction,i.e. both system and surroundings are restored to initial conditions A reversible process leaves no history of the process after it is reversed No friction involved The processes represent idealization and are never realized in real life

Reversibility and Irreversibility

A process which is not reversible is irreversible Irreversible processes have friction and are carried out with finite driving forces If a system in this case is restored to its original state, surroundings must be altered Caused by friction, unrestrained expansion, mixing of substances, combustion, flow of electricity through a resistor, heat transfer over a finite temperature difference etc.

Quasi-equilibrium process

A process in which deviation from equilibrium is infinitesimal All states through which a system passes during such a process can be considered as a succession of equilibrium states Takes place very slowly with an infinitesimal change in properties at each step Path can be described for such a process A quasi-equilibrium process without friction is reversible

Understanding Energy
Difficult to define in general, but is defined as capacity of a body to do work (causes an effect) Exists in various forms and can be converted from one form to another (partial or complete), but can never be destroyed Can be classified as energy in transition and energy in storage SI units: Joules

Understanding Energy

Energy transferred as a result of potential difference is energy is transition. Loss of identity as soon as soon as energy enters and leaves a system. E.g.: gradient of force, temperature and potential result in transfer of mechanical work, heat and electrical energy respectively Stored energy possessed by a system as a result of its position in a force field, its motion, its atomic or molecular structure etc. Examples are kinetic, rotational or vibrational energy, chemical or nuclear energy etc.

The concept of thermodynamic work

By definition it is Force times displacement, the latter measured in the direction of the force from the point of application But then thermodynamics talk of system and surroundings. Hence work needs to be defined in thermodynamic language

The concept of thermodynamic work

Work is said to be done by a system if the sole effect on the surroundings is reduced to lifting of weight Note The definition does not call for actual raising of a weight, but rather the possibility of a weight being raised Thermodynamic work is energy in transition and is manifest at the system boundary only during system-surrounding interaction. Before the interaction work is present and after the interaction no work exists

The concept of thermodynamic work

MOTOR

WORK

MOTOR

Work crosses system boundary in both cases (green and red boundaries)
Flow of electricity across a system is equivalent to work crossing the system boundary

WORK
WORK

The concept of thermodynamic work

Conventions important when solving problems In thermodynamics work done by a system is positive and work done on a system is negative System and surroundings do equal, but opposite work Wsystem + Wsurroundings = 0 Net work done by a system is expressed as Wnet = Wout - Win

Work done in a frictionless quasi-equilibrium process

Initial conditions Gas at P, T and volume V inside frictionless piston and cylinder arrangement in thermal equilibrium P exerts a force F. Under equilibrium, this is balanced by a force caused by atmospheric pressure and piston weights (-F) which results in Pext

Work done in a frictionless quasi-equilibrium process

Remove an infinitesimally small weight. This will result in reduction of pressure and slight expansion will take place. Reduced gas pressure will be balanced by reduced weights which will be raised and work will be done W = Fdz = (PA)dz = PdV

dz

Work done in a frictionless quasi-equilibrium process

Let finite weights be removed ensuring quasi-equilibrium process 1- 2 in which volume changes from V1 to V2 During this change system and surroundings are in equilibrium The net work done during the expansion 1-2 is

Final state after weights are removed

1W2

= W = PdV

Work done in a frictionless quasi-equilibrium process

The integral represents the area under the P V diagram Work done can be found by integration provided a relationship between P and V is known This is displacement work and is valid only for frictionless process This expression applies to any compressible system of any arbitrary shape

Work done in a frictionless quasi-equilibrium process

Specific work = Work per unit mass of the system W = mw = PdV = m Pd The integral can be evaluated by graphical or numerical methods (if path known from experimental data) or by curve fitting experimental data to obtain a relationship between P and V and then using direct integration

Evaluating work for some common processes

CONSTANT PRESSURE PROCESS P = CONSTANT 1W2 = W = PdV = P dV WORK DONE = P (V2 V1)
P
1 2

1W 2

Evaluating work for some common processes

CONSTANT VOLUME PROCESS V = CONSTANT, dV = 0 WORK DONE = 0
P
1

Evaluating work for some common processes

HYPERBOLIC PROCESS PV = CONSTANT = P1V1 = P2V2 1W2 = W = P1V1 (dV / V) WORK DONE = P1V1 ln(V2 / V1) = P2V2 ln(V2 / V1)
P
1
1W2

NOTE HYPERBOLIC PROCESS BECOMES ISOTHERMAL IF T IS CONSTANT, PV = RT = C V

Evaluating work for some common processes

POLYTROPIC PROCESS PVn = P1V1n = P2V2n = C The index n is the polytropic index. It can be evaluated if P and V at initial and final states are known, thus n = ln (P1 / P2) / ln (V2 / V1) The polytropic relation represents the most convenient curve fitting of actual experimental data between P and V with the value of the index n evaluated with the help of any two points on the curve

Evaluating work for some common processes

For integration purposes P = C / Vn = P1V1n / Vn = P2V2n / Vn n) W = W = C (d V / V 1 2 1n- V 1n) / 1 n W = C ( V 1 2 2 1 Substituting C = P1V1n = P2V2n from V /V = (P /P ) 1W2 = (P2V2 - P1V1) / 1 n ){(n 1) / n} 1] W = ( P V / 1 n ) [ ( P / P 1 2 1 1 2 1
2 1 2 1 1/n

Evaluating work for some common processes

n, the polytropic index can have many values. note that when n = 0, the process is constant pressure (isobaric) and when n = , it is a process at constant volume Integration valid when n 1 For hyperbolic process n = 1

Evaluating work for some common processes

If the gas is ideal, then P1V1 / T1 = P2V2/T2 A relationship between T P and V T can be obtained thus T2 / T1 = (P2 / P1)(n 1 / n) = (V1 / V2)(n 1) Putting P2V2 = mRT2 and P1V1 = mRT1 1W 2 = m R (T2 - T1) / 1 n (Polytropic work for an ideal gas)

Evaluating work for some common processes

A gas is contained in a cylinder fitted with a piston loaded with a small number of weights. The initial pressure of the gas is 1.3 bar and the initial volume is 0.03 m3. The gas is now heated until the volume increases to 0.1 m3. Calculate the work done by the gas for the a constant pressure, constant temperature process and PV1.3 = C process

Evaluating work for some common processes

CONSTANT PRESSURE PROCESS (CAUSED BY MOVING PISTON AS GAS IS HEATED) WORK DONE = P (V2 V1) = 9.1 kJ CONSTANT TEMPERATURE PROCESS (REMOVE WEIGHTS AT A RATE THAT THE TEMPERATURE REMAINS CONSTANT WHILE HEAT IS ADDED TO THE GAS) WORK DONE = P1V1 ln(V2 / V1) = 4.695 kJ

Evaluating work for some common processes

POLYTROPIC PROCESS (ACHIEVED BY REMOVING WEIGHTS AT A RATE SUCH THAT P1V11.3 = P2V21.3 DESCRIBES P V RELATIONSHIP
WORK DONE = (P2V2 - P1V1) / 1 n = 3.933 kJ
STATE 1 2 CAN BE ACHIEVED THROUGH DIFFERENT ROUTES. WORK DONE IS DIFFERENT FOR EACH PATH. WORK IS THUS A PATH FUNCTION (REMEMBER QUASIEQUILIBRIUM)

Evaluating work for some common processes

Work done in a process is not only a function of the two end states, but it also depends on the path followed in going from one state to another Work is a path function and an inexact differential Thus 1W2 = W W2 W1. Hence never speak of work in state 1 or state 2. There is only Win and Wout which is work in transition

Work done in an irreversible process

Not all processes confirm to idealized quasi-equilibrium conditions. Actual process are inherently irreversible, i.e. surroundings are altered even when system returns to original state A process maybe irreversible essentially in two ways, i.e. nonequilibrium irreversible or due to friction

Work done in an irreversible process

In a non-equilibrium process, there is a finite change. Path of the process is not known. Only end states are known In a process where friction is present quasistatic conditions can exist, i.e. Pext F/A = P Local temperature changes due to friction near piston cylinder contacts. Thermodynamic equilibrium is thus absent. Work is dissipated as heat and cannot be recovered

Work done in a nonequilibrium process

Actual case where finite weights are removed. Only initial and final states are known. The system and surroundings are not in equilibrium at each step Pext = P2
P
F
2
1
1W2

Pext = P1

Work done in a nonequilibrium process

PdV does not represent work But some work has been done because volume has changed and this is finite change, i.e. V W = Pext V (work done in a non-equilibrium process) Note pressure Pext here is external pressure and during the process never equal to P, the pressure of the gas.

Work done in a process with friction

In this case Pext + F/A = P or Pext - F/A = P is possible depending on whether expansion or compression takes place For compression Pext > P and for expansion Pext < P (P is the gas pressure) Thus in a process with friction W = PextdV (Pext = P F/A) Less work obtained during expansion and more work required during compression

Work done in an irreversible process

Lost work = PdV - PextdV It is seen that for a reversible process, for a given change of state, work output during expansion is maximum and work input during compression is minimum. In an irreversible process during expansion work output is less than maximum and during compression more than minimum An irreversible process is always inferior

Two inherently irreversible process

Free expansion where PdV is finite, but work done is zero. Finite means can be evaluated Pext = 0
Fluid, state 1, P1, V1

Vacuum, Pext = 0

Q=0 W=0

Not quasiequilibrium
PextdV = 0

Q=0 Fluid, state 2, P2, V2 W=0

No work done during free expansion

Two inherently irreversible process

MOTOR

Paddle wheel work Volume does not change and friction not involved
System boundary does not move

A situation where PdV is zero, but work is still done

The State Postulate

Simple system: A system which involves only one work mode State Postulate: The number of independent intrinsic properties required to define the state of a system is equal to one plus the number of possible work modes Thus for a simple system, the number of independent intrinsic properties required is 2

The concept of heat

In the case of paddle wheel work, temperature rises, i.e. a change of state occurs The same state can be brought about if heat entered the system instead of work Effect of heat on a system could be same as the effect of work Heat is energy as work is and has units of work

The concept of heat

Heat is thus defined as energy in transition flowing by a virtue of a temperature difference between two systems or between a system and it s surroundings It manifests only at the system boundary and cannot be contained

The concept of heat

Sign convention of heat is just opposite to that of work Heat entering a system is positive (added to) and leaving a system is negative A process in which no heat transfer takes place is an adiabatic process In a closed system an application of work or heat can cause a change of state

The concept of heat

When heat is added to a pure substance it is seen that either the phase changes with temperature remaining constant (saturation state) or temperature changes with substance remaining in the same phase In the former case it is called latent heat and in the latter sensible heat Heat transfer by 3 modes: conduction, convection or radiation

Objective Assessment
Concept of reversibility and irreversibility Concept of work Estimating work for various processes Concept of heat

There are two ways of meeting difficulties: you alter the difficulties or you alter yourself meeting them. It is better than running away from them.