Thermodynamic Systems

A thermodynamic system is a collection of matter which has distinct boundaries. OR A real or imaginary portion of universe which has distinct boundaries is called system. OR A thermodynamic system is that part of universe which is under thermodynamic study. Lagrange (Closed Systems) Vs. Eulero (Open Systems)
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Definitions
A system is the object or material(s) under study, separated from its surroundings by some specified boundary in essence, some collection of atoms. If neither matter nor energy crosses the boundary, it is an isolated system. If only energy crosses the boundary, it is a closed system. If both energy and material cross the boundary, it is an open system.

Thermodynamic process * The transformation of a system between two states describes a path, which is called a thermodynamic process. * There are infinite paths to connect two states.

Type of processes
1- Isothermal process 2- Isobaric process 3- Isochoric process 4- Adiabatic process 5- Cyclic process T = 0 P = 0 V = 0 q=0 =0

Reversible and Irreversible Processes: Reversible process: Is a process which maybe reversed at any moment by changing an independent variable by an infinitesimal amount. Irreversible Process: Is the process that will not reverse the system if any change has happened on the system.
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Extensive Properties( variables): The property which depends on the amount of the substance, such as : ( S, m, U, V, G .) Intensive properties( Variables) : The properties which are independent on the amount of substance, such as ( Temp, press, density, viscosity, chemical potential ) State of a system at equilibrium: Is defined by the collection of all macroscopic properties that are described by state variable (P, n, T, V) and independent on the history of the system.

Work force applied over a distance against a load (e.g. foot-pounds, or Newton-meters = joules) W = F . dh P= F = P. A W = P . A. dL Then W = P V W = Pext. ( V2 V1) V = A. dL gas A dh : distance F: force pex

dh

The ( +ve ) sign for work means the system achieved work on the surrounding, such as gas expansion. The (-ve) sign for work means the surroundings achieved work on the system, such as gas compression in a cylinder. 6

1- Expansion work
W = - Pex dv ( work done by the gas) Work against a constant external pressure Pex = constant P W = - Pex .dV = -Pex (V2 V1) = - Pex V V1 V2 W P1 = P2

2- Free Expansion ( Expansion against vacuum )

Pex = 0 W = - Pex .dV W= 0
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3- Isothermal Reversible expansion work

Pgas = Pex W = - Pex .dV W = - Pgas .dV for ideal gas Pgas = nRT/ V Vi If T = constant ( Isothermal) ( Isothermal reversible work ) Pf w Volume Vf Pi P=nRT/V

Example:
For evaporation of one mole of water at constant pressure at one atm and 100oC : 1- what is the work done 2- what is the change in internal energy? 1- V1 = Mwt / d = 18 ml = 0.018 lit W = -Pex (V2 V1 ) W = -1 ( 30.6 0.018) W = - 30.6 lit.atm = 30.6 *24.2 cal = 741.4cal 2- U = q + W q = 540 * 18 g U = 9720 741.4 = 8979 cal V2 calculation according to STP

Example :
what is the work of reversible expansion of a mole of ideal gas at (0oC) from ( 2.24 to 22.4) ?? Reversible and isothermal V1 = 2.24 V2 = 22.4 T= 0oC = 273oK W= ?

W= -1 x 1.987 x 273 ln 22.4/2.24 W = -1250 cal . Mol-1

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Ex: calculate the maximum work for a reversible expansion at constant temperature from an initial volume of V1 to a final volume ( 10 V1) that will do 10000 cal of work, if the initial pressure is 100 atm . 1- find V1 2- if 2 mole of gas their, what would be the temperature??

Wrev = 2.303 nRT log 10V1/V1 Wrev = 2.303 nRT P1 V1 = nRT = Wrev / 2.303 100 x V1 = 10000 / 2.303 V1 = 1.78 lit 2- W = nRT ln V2/V1 = 2.303 nRT log 10 V1 /V1 = 2.303 nRT RT = 10000/ 2x2.303 T = 1100 oK

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Heat ( q) the energy that flows from a body at higher temperature to one at lower temperature by virtue of the temperature difference. Experiments have shown that every material has a characteristic heat capacity per gram, or specific heat capacity heat capacity ( C ) amount of heat that is required to raise the temperature of the system 1oC .

If ( C ) is known , then we can determine the amount of heat required to raise the temperature of a constant mass of a system from ( T1 ) to ( T2) by: q = C ( T1 T2 ) = C T The unit of heat capacity is ( joul / mole. Kelvin)

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1st Law of Thermodynamics

Law of conservation of energy (Energy can not be destroyed nor created)

dE = q W positive q : heat added to system positive W : work done by system

statement of energy conservation for a thermodynamic system internal energy E is a state variable W, q process dependent

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Thus the first law may also be state as: the net energy change of a closed system is equal to heat transferred to the system minus the work done by the system.

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Exact differentials:
If a system is taken along path ( for example by heating it ), U changes from Ui to Uf , and the overall change is the sum (integral) of all the infinitesimal changes along the path: U = du the value of U depends on the initial and final states of the system but independent on the path between them. (Exact differential ) and U is said to be ( state function) .

Units of energy are ( J, kj, cal, kcal) 1 j = 1kg.m2.S-2

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Heat Content ( Enthalpy) ( H ):

Is the thermal change at constant pressure. ( the amount of heat absorbed or emitted by a reaction).

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H = E + P V + V P
at constant ( P ) P = 0

H = E + P V
From first law of thermodynamics

E = q - w E = q - P V
So... q = E + P V
Substitute in the equation above :

H = qp

At constant prerssure

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dE = Cv dT

dE = Cv dT E2 E1 = E = Cv dT E = Cv ( T2 T1 ) E = Cv T E = n Cv T ( for n= 1 )

if Cv = constant , then

( for n moles)
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dH = Cp dT

In the same way as for Cv : when Cp is constant , then : H = n Cp T

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The variation of heat capacity with temperature can sometimes be ignored if the temperature range is small; this approximation is highly accurate for a monatomic perfect gas (for instance, one of the noble gases at low pressure). However, when it is necessary to take the variation into account, a convenient approximate empirical expression is:
Cp,m = a + bT + c T2

The empirical parameters a, b, and c are independent of temperature

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Example : Cp = a + bT + c T2 + .. dH = n Cp dT H2 - H1 = n ( a + bT + cT2 ) dT n=1

H = a .dT + bT .dT + c T2. dT

= a ( T2 - T1) + b ( T 2 - T2 ) + 2 1 2
3 3 c ( T2 - T1 ) 3

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Example / What is the change in molar enthalpy of N2 when it is heated from 25C to 100C? Use the heat capacity information in Table 2.2Cp,m = a + bT +

Method The heat capacity ofN2 changes with temperature, so we cannot use eqn 2.23b (which
assumes that the heat capacity of the substance is constant). Therefore, for the temperature dependence of the heat capacity, and integrate the resulting expression from 25C to 100C.

c T2

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Example : The equation for the molar heat capacity for n-butane is ( Cp 4.64 + 0.0558 T ). Calculate the heat necessary to rise the temperature of 1 mole of the Butane from 25 to 300oC at constant pressure. dH = n Cp dT H2 - H1 = ( 4.64 + 0.0558 T ) dT H2 - H1 = 4.64 ( T2 T1 ) + 0.0558/ 2 ( T22 - T12 ) H = (4.64 (300 -25) + 0.0558/ 2 ( 5732 - 2982 ) = 7959 Cal mol-1

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The Molecular Interpretation of the Internal Energy

1- For ideal gas, the only energy is the translational kinetic energy of the molecules, and it will be found that the energy of the model gas of N molecules is

2- for Real gas , total Energy = Transitional energy + Internal Energy Real atoms and molecules are not structureless particles. Real atoms and molecules have translational energy and electronic energy, and molecules also have rotational and vibrational energy. 3- Internal Energy = Erot + Evib So

Etotal = Etrans + Erot + Evib

Etot = 3/2 RT + 1/2 RT + 1/2RT

4- Evib consist of two type, each contribute by 1/2RT , so 2 x 1/2RT = RT 5- For linear molecules, there are two axis of rotation, each contribute by 1/2RT For non-linear molecules, there are three axis of rotation, each contribute by 1/2RT
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Internal energy = 3N 3 Evib = 3N 5 = 3N 6

N : no of atoms in the molecule

7- Evib

-------------- ( for linear molecules ) -------------- ( for non-linear molecules)

Example : calculate Cv for a linear diatomic molecule .

Etot = Etrans + Einternal Etrans = 3 x 1/2 R T = 3/2 RT Erot = 2 x 1/2 RT = 1 R T Evib = (3 N 5 ) x R T Evib = (3 x 2 - 5 ) x RT = 1 R T Etot = 3/2 RT + RT + RT Etot = 7/2 RT Cv = 7/2 R Cv = dE / dT
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1/2 R T for each axis 1/2 RT each axis( linear molecule have 2 axis of rotation) there are 2 types of vibrations ( 2 x 1/2 RT = R T)

Adiabatic changes We are now equipped to deal with the changes that occur when a perfect gas expands adiabatically. A decrease in temperature should be expected: because work is done but no heat enters the system, the internal energy falls, and therefore the temperature of the working gas also falls. In molecular terms, the kinetic energy of the molecules falls as work is done, so their average speed decreases, and hence the temperature falls. The change in internal energy of a perfect gas when the temperature is changed from Ti to Tf and the volume is changed from Vi to Vf can be expressed as the sum of two steps (Fig. 2). In the first step, only the volume changes and the temperature is held constant at its initial value. However, because the internal energy of a perfect gas is independent of the volume the molecules occupy, the overall change in internal energy arises solely from the second step, the change in temperature at constant volume. Provided the heat capacity is independent of temperature, this change is E = Cv T

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Because the expansion is adiabatic, we know that q = 0; because E = q- w , it then follows that E = - w . Therefore, by equating the two values we have obtained for E, we see that w = - Cv T

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Example :- A system consisting of 2.000 mol of argon expands adiabatically and reversibly from a volume of 5.000 L and a temperature of 373.15K to a volume of 20.00 L. Find the final temperature. Assume argon to be ideal with CV equal to 3nR/2.

Example :- Find the volume to which the system of the previous example must be adiabatically and reversibly expanded in order to reach a final temperature of 273.15 K.
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Example: a sample of Ar at one atm press and 25oC expands reversibly and adiabatically from (0.5 to 1 Lit). Calculate the final temperature and the work done during this expansion. Given that the molar heat capacity of Ar= 12.48 J/K mol-1. P1 =1atm Cv =12.48 V1 =0.5 L 1) T2 =? T1 =25oC T2 = ? V2 =1L 2) w = ? 3) E

V1T1Cv/R = V2 T2Cv/R T2 = ( V1/V2)R/Cv .T1 T2 = ( 0.5/1)1/1.5 x 298 = 188oK For adiabatic process w = CvdT = Cv T PV=nRT n = ( 1x 0.5) / (0.0821x298) = 0.02 mol 2) W = nCv T = 0.02 x 12.48 x (188 298) W = -27 j 3) E = q w q=0 E = W = -27 J

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Thermochemistry
The study of the energy transferred as heat during the course of chemical reactions is called thermochemistry. Thermochemistry is a branch of thermodynamics because a reaction vessel and its contents form a system, and chemical reactions result in the exchange of energy between the system and the surroundings. Thus we can use calorimetry to measure the energy supplied or discarded as heat by a reaction, and can identify q with a change in internal energy (if the reaction occurs at constant volume) or a change in enthalpy (if the reaction occurs at constant pressure). Conversely, if we know U or H for a reaction, we can predict the energy (transferred as heat) the reaction can produce.

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The Truth about Enthalpy

1. Enthalpy is an extensive property. 2. H for a reaction in the forward direction is equal in size, but opposite in sign, to H for the reverse reaction. 3. H for a reaction depends on the state of the products and the state of the reactants.
Thermochemistry

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Standard enthalpy changes

Changes in enthalpy are normally reported for processes taking place under a set of standard conditions. In most of our discussions we shall consider the standard enthalpy change, Ho, the change in enthalpy for a process in which the initial and final substances are in their standard states: The standard state of a substance at a specified temperature is its pure form at 1 bar. For example, the standard state of liquid ethanol at 298 K is pure liquid ethanol at 298 K and 1 bar; the standard state of solid iron at 500 K is pure iron at 500 K and 1 bar. The standard enthalpy change for a reaction or a physical process is the difference between the products in their standard states and the reactants in their standard states, all at the same specified temperature.

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Different types of Enthalpies of physical change

The standard enthalpy change that accompanies a change of physical state is called the standard enthalpy of transition and is denoted trsHo. The standard enthalpy of vaporization, vapHo, is one example. Another is the standard enthalpy of fusion, fusHo, the standard enthalpy change accompanying the conversion of a solid to a liquid, as in

Because enthalpy is a state function, a change in enthalpy is independent of the path between the two states. This feature is of great importance in thermochemistry, for it implies that the same value of I'1H-e- will be obtained however the change is brought about between the same initial and final states. For example, we can picture the con- version of a solid to a vapour either as occurring by sublimation (the direct conversion from solid to vapour),
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or as occurring in two steps, first fusion (melting) and then vaporization of the result- ing liquid:

Because the overall result of the indirect path is the same as that of the direct path, the overall enthalpy change is the same in each case, and we can conclude that (for processes occurring at the same temperature)

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Hess's law
The standard enthalpy of an overall reaction is the sum of the standard enthalpies of the individual reactions into which a reaction may be divided. The individual steps need not be realizable in practice: they may be hypothetical reactions, the only requirement being that their chemical equations should balance.

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Standard enthalpies of formation The standard enthalpy of formation, fHo, of a substance is the standard reaction enthalpy for the formation of the compound from its elements in their reference states. The reference state of an element is its most stable state at the specified temperature and 1 bar. For example, at 298 K the reference state of nitrogen is a gas of N2 molecules, that of mercury is liquid mercury, that of carbon is graphite, and that of tin is the white (metallic) form. Standard enthalpies of formation are expressed as enthalpies per mole of molecules or (for ionic substances) formula units of the compound. The standard enthalpy of formation of liquid benzene at 298 K, for example, refers to the reaction 6C(s, graphite) + 3H2(g) -- 7C6H6(l) and is +49.0 kJ mol-I. The standard enthalpies of formation of elements in their reference states are zero at all temperatures.
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