Chapter 1. the First Law of Thermodynamics for Close System Key Learning Outcomes Know different types of energy.

nergy. Understand conservation of energy principle. Explain internal energy and enthalpy. Know different modes of heat transfer. Understand energy transfer by work. Understand the first law of thermodynamics and apply the first law to calculate specific heat and molar heat capacity in constant volume process and constant pressure process. Understand isothermal process, reversible process and adiabatic process.

1.1 Thermodynamic System A thermodynamic system -- a quantity of matter or a region in space chosen for study. The mass or region outside the system is the surroundings. The interface separating system from its surroundings is the boundary (zero thickness in mathematical sense) and may be fixed or movable. A closed system (control mass) consists of a
fixed amount of mass and no mass can cross its boundary. But energy can cross the boundary by means of heat or work transfer. A special case, isolated system no energy is allowed to cross the boundary.

 An open system (control volume) is a properly selected region in space. Both mass and energy can cross the boundary of a control volume, e.g. water heater.

1.2 Properties and State of a System Properties are macroscopic characteristics of a system, such as mass m, volume V, pressure P, temperature T, thermal conductivity and expansion coefficient, viscosity, elastic modulus, electric resistivity, etc. Some are defined in terms of other ones, such as density m = (kg/m3) and specific volume = V (m3/kg). V m

Intensive properties independent of the size of a system, such as T, P, , etc. Extensive properties proportional to the size of the system, m, V, etc.

Specific properties extensive properties per unit mass. Non- (thermodynamic) properties: mass flow rates and energy transfers by work and heat, etc.

The state of a system can be specified in terms of state variables, V, P, T and m, etc. For a given state, all the thermodynamic properties have definite, unique values.

But the properties are not all independent. Specifying a certain number of properties is sufficient to fix a state. State postulate: The state of a simple compressible system is completely specified by two independent, intensive properties.

Equilibrium state overall system does not undergoing any change and all state variables stay constants. It is a dynamical equilibrium. Thermal equilibrium same temperature throughout the entire system. Mechanical equilibrium no change in pressure at any point of the system with time. Phase equilibrium the mass of each phase in a multiphase system stays at a constant. Chemical equilibrium chemical composition does not change with time.

1.3 Thermodynamic Process and Cycle Thermodynamic process any change that a system undergoes from one equilibrium state to another. Path of a process a system passes through a succession of states during a process. Change in value of a property in a
process depends only on the two end states and is independent of the process path. A quantity is a thermodynamic property if, and only if, its change in value in a process is independent of the process path. Quasi-static or quasi-equilibrium process.

Thermodynamic cycle a sequence of processes that begins and ends at the same state.

1.4 Energy, Type of Energy and Conservation of Energy Mechanical energy

Electrical energy Magnetic energy Chemical energy Nuclear energy -- the complete fission of 1 kg uranium-235 releases 6.731010 kJ of heat (> heat from 3000 tons coal). The macroscopic forms of energy are those a system possesses as a whole with respect to some outside reference frame, and are related to motion and the influence of some external effects such as gravity, magnetism, electricity and surface tension, etc. Kinetic energy: as a results of the motion of the system relative to some reference frame. KE = mv2/2 Potential energy: as a results of its elevation in a gravitational field. PE = mgz

 The microscopic forms of energy are those related to the molecular structure of a system and the degree of the molecular activity, and they are independent of outside reference frames. The internal energy is the sum of all the microscopic forms of energy, U. The conservation of energy principle states that during an interaction, energy can change from one form to another but the total amount of energy remains constant. E=U+KE+PE=U+ mv2/2+mgz

1.5 Modes of Heat Transfer

Heat -- the form of energy that is transferred between a system and its surroundings brought about by a temperature difference. The formal sign convention for heat, Q>0, heat transfer to the system (input - endothermic) Q<0, heat transfer from the system (output - exothermic) Q=0, an adiabatic process and no energy transfer by heat. Q has the unit of energy, i.e. Joule.

Conduction

Convection

Radiation

1.6 Energy Transfer by Work

Work -- an interaction between a system and its surroundings. The interaction is not caused by a temperature difference between a system and its surroundings. The formal sign convention for work, W>0, work done by a system (output) W<0, work done on a system (input) W has the unit of energy, e.g. J (Joule) and kJ. Work done per unit time is power and the unit of power is J/s and kJ/s

Heat and Work have many similarities: Heat and work are boundary phenomena Systems possess energy, but not heat or work Heat and work are associated with a process, not a state. They are path functions. Unlike properties, they have no meaning at a state.

Kinetic Energy: Body of mass m (a system) moves in x direction with a velocity v under the action of a force F (the surroundings). Newton's 2nd law gives, F=massacceleration dv dv dx dv F =m =m = mv dt dx dx dt x2 v2 1 2 2 Fdx = mvdv = m v2 v1 2 x1 v1 where v1 and v2 are the velocity of body at x=x1 and x=x2, respectively x2 Fdx = W work done by F to the system (1 Nm=1 J)

x1

Power, W is the rate of energy transfer by work from the system to the surroundings: W = dW = dW dx = Fv J/s = W dt dx dt

1 2 2 m v2 v1 =kinetic energy (KE) change=KE 2

(Watt)

Potential Energy: Body moves vertically under the action of the weight force mg and an applied force R. Work done by resultant force (R-mg) is
h2 h1

(R -m g ) d h = Rdh mg (h2 -h1 )

h1

h2

where mgh is the potential energy (PE) of the body. Thus, Rdh - PE = KE, i.e. - W = PE + KE where W= - R dh is the work done by R on the body.
h1 h2
h1 h2

If R=0, (PE + KE)=0 and the sum of KE and PE remains constant.

Strain Energy

Undeformed spring Deformed spring The system: body+spring (obeys Hooke's law R=kx). 1) As the spring extends slowly:
2 -W = R dx = k (x2 x12 ) =SE x2 x1

1 2

where

1 2 kx 2

is the strain energy (SE) in the spring.

2) If spring extends at a finite rate: -W=SE+KE=(SE+KE) 3) If motion of body has a vertical component: -W=(SE+KE+PE)

Expansion of a Gas in a Cylinder: System: gas with a pressure P is confined by a piston sliding without friction in a cylinder. Work done by the system (i.e. the gas) as volume V of gas changes is

W = PAdx = PdV
1) Expansion: dV>0, W>0. Work is done by the system on the surroundings 2) Compression: dV<0, W<0. Work is done by the surroundings on the system
The Work done by the system in the process 1-2 is represented by the area under the P-V curve. Since this area depends on the process path and not just the end states, it follows that W is not a property of the system.
x1 V1

x2

V2

Shaft work -- energy is transmitted via a rotating shaft carrying a torque T=Fr. When the shaft rotates through an angle (radian), the shaft work can be calculated by Ws=Force Distance=F(r)=T. The power transmitted is given by
Ws =

where is the angular velocity in rad/s. If 2 n n is the speed in rev/min then = rad/s.
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dWs d (T ) d = =T =T dt dt dt

Stirring Work - Ws=T

Electrical Work Non-mechanical forms of work. In an electric field, electrons moving in a wire driven by electromotive forces, doing work. Consider Q coulombs of electrons move through a potential difference V, the work done is We=QV, J (Joule)

We =

dWe dQ = V = IV dt dt

J/s = W (Watt)

1.7 The First Law of Thermodynamics Statement: energy can be neither created nor destroyed; it can only change forms. For a cyclic process: Net heat input - Net work output = 0

cycle

Q W = (Q W ) = 0
cycle cycle

where Q and W are energy transfers by heat and work for the various processes in the cycle.

Consider a cyclic process 1A2B1 as shown in the figure:

cycle

(Q W ) = (Q W ) + (Q W ) = 0
1 A2 2 B1

if A' is an alternative process path between State 1 and 2, then

1 A' 2

(Q W ) + (Q W ) = 0
2 B 1
1 A2 1 A' 2

Thus (Q W ) = (Q W ) Define Q = Q and W = W . The value of (Q-W) is independent of the process path. Therefore, a property E, the total energy of system can be defined in terms of Q-W=E2-E1=E

E is comprising of KE, PE and the internal energy U: E = KE + PE + U KE =

1 2 2 m v2 v1 and PE = mg (h2 h1 ) 2

U = m (u2 u1 ) where u is the specific internal energy (kJ/kg). For an infinitesimal energy changes in time interval dt: dQ - dW = dE For stationary systems KE =0 and PE =0: dQ - dW = dU or, in the rate form, as
dQ dW dE or Q W = U = dt dt dt

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1.8 Applications of the First Law of Thermodynamics Specific Heat - For a body of mass m, the energy dQ required to raise the temperature by dT is given by: dQ = mCdT where C is the specific heat of a substance, i.e. the amount of energy required to raise the temperature of a unit mass of a substance by one degree (K or oC) in a specified way.

If dQ=nCmdT, Cm is the molar heat capacity. The value of C depends on the nature of the process undergone during the energy transfer.

1.8.1 Constant Volume Process The 1st Law: dQ-dW=dU

where dW=PdV=0 and dQ=mCvdT =dU The heat transfer at constant volume is equal to the change of internal energy. Thus: mCvdT=dU or Cv =
1 U kJ/(kg K) m T v

Cv is the change in internal energy of a unit mass of a substance with temperature at constant volume. But for ideal gas: U=U(T), hence, Cv = m dT
1 dU

Now dQ=dU= mCvdT Thus Q = U = U 2 U1 = mCv dT mCv (T2 T1 )

T1 T2

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1.8.2 Constant Pressure Process The 1st Law: dQ-dW=dU since dW=PdV dQ = PdV + dU As P is a constant: PdV=d(PV) hence dQ = d(PV) + dU = d(PV+U) Define a new (combination property), the enthalpy of the system: H=U+PV ; unit: kJ=kJ+kPam3(=kJ). dQ=dH The heat transferred at constant pressure is equal to the enthalpy change.

An extensive property A thermodynamic state function Arbitrary zero.

By definition, dQ= mCpdT =dH, hence

CP = 1 H m T P

kJ/(kg K)

Cp is the change in enthalpy of a unit mass of a substance with temperature at constant pressure. For an ideal gas: H=H(T), and CP = Now dH=mCpdT, thus
T2 T1

1 dH m dT

H = H 2 H1 = mC p dT mC p (T1 T2 )

However Cp is, in general, a function of temperature. For gases at low pressure, Cp is often expressed as a polynomial in T the so-called ideal gas molar heat capacities.

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C p = A + BT + CT 2 + Where A, B, C,. are constants obtained by fitting to experimental data. Thus,

T h(T ) = h(T0 ) + T A + BT + CT 2 + dT
0

= h(T0 ) + A(T T0 ) +

B 2 T T02 2

) )+ C (T 3

T03 +

For simplicity, we often use mean molar heat capacities defined as follows. T
C Pm

T0

C P dT

T T0

When tabulated values of h(T0) and Cpm are available, we can readily calculate

h(T ) = h(T0 ) + CPm (T T0 )

Illustration Calculate the mean molar heat capacity of methanol between 25 and 250 C. The ideal heat capacity is given by the following equation:

where A = 18.38, B = 0.1016 and C = 2.868 105 (CP in J K1 mol1, T in K). T Solution: T CP dT
C Pm =
0

C P = A + BT + CT 2

T0

C P dT = A + BT + CT 2 dT
T0

B 2 C T T02 + T 3 T03 2 3 2 = 18.38(225) + 0.0508 523 2982 0.956 10 5 5233 2983 = A(T T0 ) +

= 12.405 10 J mol
3

C Pm = 12.405 103 / 225 = 55.1 J K 1 mol 1

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1.8.3 Relationship between Cp and Cv for the Ideal Gas Model For a constant pressure process: dQ = dW + dU i.e. mCpdT = PdV + dU

CP =

P dV 1 dU + m dT m dT
Cv = 1 dU m dT v

Now PV = mRT and Therefore:

Cp =

P d mRT 1 dU = R + Cv + m dT P m dT
CP CV

Hence C P CV = R kJ/(kg K) The specific heat ratio

=

(=5/3 for the ideal gas model)

1.8.4 Isothermal Expansion Process for Ideal Gas

If T = constant then since U = U(T) for ideal gas, dU=0 and dQ dW = dU =0, where dW=PdV and PV = mRT . Thus,
Q = W =
V2

V P mRT dV = mRT ln 2 = mRT ln 1 V P V1 V 1 2

Mechanical equilibrium with the surroundings is maintained. In the expansion, the external pressure must be continuously adjusted so that it is just slightly smaller than the system pressure. This is an example of a reversible process. It can be reversed in either direction by an infinitesimal change in Pex. A system does maximum expansion work when it is in mechanical equilibrium with its surroundings at every stage of the expansion.

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1.8.5 Adiabatic Process Since dQ=0, it follows that: -dW = dU = mCvdT

now dW=PdV and PV = mRT

mCv dT = m
T2

RT dV V

C C note: R = p v = 1 Cv Cv

V2 T V dT dV = ( 1) ln 2 = ( 1)ln 2 T 1 V1 T1 T V1 V

T1 V2 = T2 V1

T1V1 1 = T2V2 1 P V1 = P2V2 1

1 1 T1P 1 1 1 = T2 P2

P V1 1 P2V2 1 1 V2 V1 = mR mR mRT1 mRT2 P = P2 1 P P 2 1

Illustration: Evaluate the final temperature when 1 mol of N2 is expanded adiabatically to 10 times its original volume. The initial temperature is 0 C. Cv = 20.8 J K1 mol1. How much work is done? Solution: T 8.314 ln 10 = 0.9204 dQ=0, the 1st law gives ln 2 = T1 20.8 -dW = dU = mCvdT
T R V2 ln 2 = ln T Cv V1 1

T2 = 0.398 273
T2 = 109 K

W = nC V (T2 T1 ) = 20.8(109 273)

W = 3410 J

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Key Learning Outcomes Know different types of energy. Understand conservation of energy principle. Explain internal energy and enthalpy. Know different modes of heat transfer. Understand energy transfer by work. Apply the first law of thermodynamics to calculate specific heat and molar heat capacity in constant volume process and constant pressure process. Understand isothermal process, reversible process and adiabatic process.

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