MODULE 2

The First Law and Other Basic Concepts

Relevant definitions
1. System: Portion of the universe that is under consideration; 2. Surroundings: the rest of the universe; 3. Boundary: the invisible and infinitesimally thin surface that separate the system from the surroundings; 4. Isolated system: cannot exchange energy or matter with the surroundings;

Relevant definitions

Relevant definitions
Example for isolated system: A perfect thermal flask would be a good example, unfortunately does not exist.

Relevant definitions
5. Closed system: can exchange energy, but not matter, with the surroundings; 6. Open system: can exchange both energy and matter with the surroundings; 7. Adiabatic system: can exchange work, but not heat or matter, with its surroundings

Example for closed system (Refrigerant circuit)

What system is this?

Relevant definitions
8. Property of a system: a macroscopic characteristic of the system; 9. Extensive property: value is additive, and proportional to quantity of matter (examples: total mass, total volume, total energy); 10. Intensive property: value independent of quantity of matter (examples: density, pressure, temperature, etc); If you put two identical objects of temperature T together, the assembly has temperature T instead of 2T)

First Law of Thermodynamics

It is an expression of the principle of conservation of energy which states that:

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.

Energy balance for closed systems

All energy exchanged between a closed system and its surroundings appears as heat and work.

U Q W
t

(2.1)

Q =Energy transferred to or from the system as heat; W=Energy transferred to or from the system as work; U= Internal energy of the system

Numerical values of Q and W are + for transfer into the system from the surroundings

Internal Energy
Internal energy refers to energy of the molecules internal to the system. It includes: - Kinetic energy due to the motion of particles (translational, rotational, vibrational); - Potential energy associated with vibrational and electric energy of atoms within molecules or crystals. It does not include energy that it may possess as a result of its macroscopic position or movement

For differential changes, the energy balance of a closed system is written as:

dU dQ dW
t

(2.2)

Using intensive properties, Eqt. (2.1) and (2.2) become:

(nU ) nU Q W
d (nU ) ndU dQ dW

(2.3)
(2.4)

Note: The absolute value of internal energy is unknown, only the changes in internal energy can be determined

Example 2.1
Water flows over a waterfall 100 m in height. Take 1 kg of water as the system and assume that it does not exchange energy with its surroundings. (a) What is the potential energy of the water at the top of the falls with respect to the base of the falls?; (b) What is the kinetic energy of the water just before it strikes bottom? (c) After the 1 kg of water enters the river below the falls, what change has occurred in its state?
p22

THERMODYNAMIC STATE AND STATE FUNCTIONS

Thermodynamic state = Set of values of properties (state variables) of a thermodynamic system that must be specified to reproduce the system. State variable/parameter = Measurable property required to describe the state of system, for example: T, P, V, mass, density, Energy, etc. Once a minimum number of variables have been specified, values of all other properties of the system become automatically fixed

Once a minimum number of variables have been specified, values of all other properties of the system become automatically fixed. For example N2 gas at a temperature of 300K and a pressure of 1 atm has a fixed volume or density or a fixed molar internal energy.

 State functions A property whose values depend on only the state of the system and not on the path by which the change from initial to final state is brought about is called state function. The change in the value of the state functions depends only upon the initial and final state the system. Some common state functions used in thermodynamics are, pressure (P), volume (V), temperature (T), internal energy (U), enthalpy (H), entropy (S), free energy (G) etc.

Example 2.2
When a system is taken from state a to state b in figure below along path acb, 100 J of heat flows into the system and the system does 40J 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 in thermo: - Absence of change; - Absence of any tendency toward change on a macroscopic scale. We can have: thermal equilibrium, mechanical equilibrium, chemical equilibrium etc.

Equilibrium
Thermal equilibrium: Occurs when a systems macroscopic thermal observables have ceased to change with time; Mechanical equilibrium: Occurs when the sum of all forces on all particles of the system is zero, and also the sum of all torques on all particles of the system is zero; Chemical equilibrium: occurs when chemical activities or concentrations of the reactants and products have no net change over time. Usually, this would be the state that results when the forward chemical process proceeds at the same rate as their reverse reaction.

Phase rule
For any system at equilibrium, the number of independent variables that must be arbitrarily fixed to establish its intensive state is given by the Gibbs phase rule:

F 2 N
= number of phases; N = number of chemical species; F= degree of freedom

(2.5)

The intensive state of system at equilibrium is established when its temperature (T), Pressure (P) and the compositions of all phases are fixed. F, the degree of freedom gives the minimum number of variables from the above set which must be arbitrarily specified to fix all remaining phase-rule variables. When F = 0 the system is invariant

Example 2.3
Determine the degree of freedom for each of the following systems (a) Liquid water in equilibrium with its vapour; (b) Liquid water in equilibrium with a mixture of water vapor and nitrogen; (c) A liquid solution of alcohol in water in equilibrium with its vapor.

Reversible process
A process is reversible when its direction can be reversed at any point by an infinitesimal change in external conditions without loss or dissipation of energy.

A reversible process
Is frictionless; Is never more than differentially removed from equilibrium; Traverses a succession of equilibrium states; Is driven by forces whose imbalance is differential in magnitude; Can be reversed any point by differential change in external conditions; When reversed, retraces its forward path, and restores the initial state of system and surroundings.

Exercise
Derive the expression of work of compression or expansion of a gas caused by the differential displacement of a piston in a cylinder.
Solution Refer to module 1

dW PdV

(2.6)

Remarks
The reversible process is ideal in that it can never be fully realized; it represents a limit to the performance of actual processes.
Results for reversible processes in combination with appropriate efficiencies yield reasonable approximations of the work for actual processes

Example 2.4
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 pressure of 14 bar. The initial gas volume is 0.03 m3. The external force on the piston is reduced gradually, and the gas expends isothermally as its volume doubles. If the volume of the gas is related to its pressure so that the product PV is constant, what is the work done by the gas in moving the external force? How much work would be done if the external force were suddenly reduced to half value instead of being gradually reduced?

Constant V and constant P processes

The energy balance of a closed system of n moles is

d (nU ) dQ dW

(2.4)

For a mechanically reversible closed system process the infinitesimal work is given by:

dW PdV Pd (nV )
t

(2.7)

(2.7) in (2.4) yields:

d (nU ) dQ Pd (nV )

(2.8)

d (nU ) dQ Pd (nV )

(2.8)

(2.8) is the general First Law equation for a Mechanically reversible, closed-system process

Constant V process t (2.8) becomes: d (nV ) dV 0

d (nU ) dQ
After integration we have:
(2.9)

Q nU

(2.10)

For a mechanically reversible, constant volume, Closed system process, the heat transferred is equal to the internal energy change of the system

Constant P process
d (nU ) dQ Pd (nV ) dQ d (nU ) Pd (nV ) d (nU ) d (nPV )

dQ d[n(U PV )] d (nH )
After integration we have:

(2.11) (2.12)

Q nH

Where H U PV is the enthalpy of the system For a mechanically reversible, constant pressure, Closed system process, the heat transferred is equal to enthalpy change of the system

Enthalpy
The enthalpy H=U+PV is also a state function as U, P and V are all state function; As U, P and V, H is an intensive property of the system; The differential form of H is given by:

dH dU d (PV )

(2.13)

After integration we have:

H U (PV )

(2.14)

Example 2.5
Calculate U and H for 1 kg of water when it is vaporised at the constant temperature of 100C and the constant pressure of 101.33 kPa. The specific volumes of liquid and vapor water at these conditions are 0.00104 and 1.673 m3kg-1. For this change heat in the amount of 2256.9 kJ is added to the water

Heat capacity
dQ C dT
Heat capacity at constant volume, Cv
(2.15)

U Cv ( )v T

(2.16)

For a constant-volume process in a closed system, (2.16) can be written as:

dU Cv dT

(2.17)

The integration of 2.17 yields:

U Cv dT
T1

T2

(2.18)

(2.10) can now be written as:

Q nU n Cv dT
T1

T2

(2.19)

(2.19) is only valid for a constant-volume process .

Notes: State function like U in (2.18) are independent of the process, i.e. it only depends on the initial and final conditions but heat and work depends on the process path. For the calculation of property changes, an actual process may be replaced by any other process which accomplishes the same change in state.

Heat capacity
Heat capacity at constant pressure, Cp

H CP ( )P T

(2.20)

For a constant-pressure process in a closed system, (2.20) can be written as:

dH CP dT
The integration of (2.21) yields:

(2.21)

H CP dT
T1

T2

(2.22)

(2.12) can now be written as:

Q nH n Cv dT
T1

T2

(2.23)

Example 2.6
Air at 1 bar and 298.15K is compressed to 5 bar and 298.15K by two different mechanically reversible processes: (a) Cooling at constant pressure followed by heating at constant volume; (b) Heating at constant volume followed by cooling at constant pressure. Calculate the heat and work requirements and U and H of the air for each path. The following heat capacities for air may be assumed independent of temperature: Cv=20.78 and Cp=29.10 J mol-1K-1. Assume also for air that PV/T is a constant, regardless of the changes it undergoes. At 298.15K and 1 bar the molar volume of air is 0.02479 m3 mol-1

Mass and Energy balances for open systems

Measures of flow:
Mass flow rate: Molar flow rate:

. m . n

Volumetric flow rate: q Velocity: u

Relations of measures of flow

. . m=M n
q=uA

. m=uA . n=uA

A = cross sectional area of a conduit;

M = molar mass; = specific or molar density; u = average speed of a stream in the direction normal to A

Mass balance for open systems

Start by defining the thermodynamic system for which mass and energy balance are written. For open systems this system is called control volume which is separated from its surrounding by a control surface.

m1
o

Control surface

Control volume

m3
d (mCV ) m m m 0 3 1 2 dt
o
o o o

m2
d (mCV ) m m m 3 1 2 dt
o o o

(m)
o d (mCV ) (m) 0 fs dt

fs

d (mCV ) ( uA) 0 fs dt

(2.24)

Continuity Equation

Steady state conditions

d (mCV ) ( uA) 0 fs dt
( uA)
fs

(2.25)

The General Energy balance

Q
Control volume 2 1 P2 , V 2 , U 2 , H 2 , u 2
o

P1 , V 1 , U 1 , H 1 , u 1

WS

o o o d (mU )CV 1 2 1 2 [(U u zg ) m]1 [(U u zg ) m]2 Q work _ rate dt 2 2

d (mU )CV dt

o 1 2 [(U u zg ) m] fs 2 o o 1 2 [(U u zg ) m] fs Q work _ rate 2

(2.26)

The General Energy balance

Q
Control volume 2 1 P2 , V 2 , U 2 , H 2 , u 2
o

P1 , V 1 , U 1 , H 1 , u 1

WS
o

work _ rate [( PV ) m] fs W [( PV ) m] fs Work associated with moving the flowing streams

o

through entrances and exits

W Include shaft work, work associated with expansion or
o

Contraction of the control volume and stirring work

The General Energy balance

Q
Control volume 2 1 P2 , V 2 , U 2 , H 2 , u 2
o

P1 , V 1 , U 1 , H 1 , u 1

WS

o o o o d (mU )CV 1 2 [(U u zg ) m] fs Q [( PV ) m] fs W dt 2 o o o d (mU )CV 1 2 [(U PV u zg ) m] fs Q W dt 2

o o o d (mU )CV 1 2 [( H u zg ) m] fs Q W dt 2

(2.27)

For applications where kinetic and potential energy changes in the flowing streams are negligible we have:
o o o d (mU )CV 1 2 [( H u zg ) m] fs Q W dt 2

o o o d (mU )CV [( H m] fs Q W dt

(2.28)

Example 2.7
An insulated, electrically heated tank for hot water contains 190 kg of liquid water at 60oC when a power outage occurs. If water is o withdrawn from the tank at a steady rate of m = 0.2 kg s-1, how long will it take for the temperature of the water in the tank to drop from 60 to 35oC? Assume that cold water enters the tank at 10oC, and that heat losses from the tank are negligible. For water let Cv=Cp = C, independent of T and P.

Energy Balances for Steady-state Flow Processes

o o o d (mU )CV 1 2 [( H u zg ) m] fs Q W S dt 2 o o o 1 2 [( H u zg ) m] fs Q W S 2

(2.29)

For single entrance stream and single exit stream we have:

o o o 1 2 [( H u zg ) m] Q W S 2
o o

(2.30)

Q WS Q W 1 2 [( H u zg )] o s o 2 m m
1 H u 2 gz Q WS 2
(2.31)

Energy Balances for Steady-state Flow Processes

1 H u 2 gz Q WS 2
(2.31)

Equation 2.31= First law for a steady-state, steady-flow process between one entrance and one exit. In applications where kinetic and potential energy terms are negligible we have:
H Q WS
(2.32)

Homework
Read and understand the principle of a flow calorimeter for Enthalpy Measurements

Example 2.8
Air at 1 bar and 25oC enters a compressor at low velocity, discharges at 3 bar, and enters a 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?

Example 2.9
Water at 200(F) is pumped from a storage tank at the rate of 50 (gal)(min)-1. The motor for the pump supplied work at the rate of 2(hp). The water goes through a heat exchanger, giving up heat at the rate of 40000 (Btu)(min1), and is delivered to a second storage tank at an elevation 50(ft) above the first tank. What is the temperature of the water delivered to the second tank?