5-1 By withdrawing heat from a system, work can Introduction be performed through the transformation of heat energy into

mechanical
energy. But as a consequence of the second law of thermodynamics, a continuous process for accomplishing this transformation will not produce a quantity of work that is exactly equivalent to the heat provided. Losses occur in such transformations, so that the problem lies in determining how to attain maximum efficiencies in converting internal energy into work and how to evaluate the quantity of energy available for work. As shown in Chapter 4, the best way to utilize internal energy to do work involves a reversible heat engine (Carnot engine). The second law indicates, however, that the efficiency of such conversions is always less than unity. In order to determine how much work-energy can be provided in a process, it is necessary to describe the available energy with respect to some reference datum. One choice could be the lowest temperature to which the system may be reduced. In the cse of the Carnot cycle, for . example, this datum is the constant temperature at which heat is rejected. The concept of availability provides the information needed to determine the maximum work that a system in a given state can perform with respect to the environment. The internal energy of a system may be divided into two parts: available energy, which under ideal conditions may be completely converted to work, and unavailable energy, which is usually discarded from the system as heat. In the case of the Carnot engine, the quantity [( Th is the available energy and the quantity (TcjTb) QsuWma is the unavailable energy. As previously shown, these two quantities may be represented by rectangular areas for the Carnot cycle, on the T-5 diagram. In engines that are less efficient than the Carnot engine, only part of the available energy is converted into work, so that the degree of conversion depends also on the efficiency of the engine. J. W. Gibbs is credited as the originator of the availability concept. He indicated that the environment plays an important part in evaluating the amount of work that can be performed by a system in any given state. According to Gibbs, the availability analysis of a process considers the system to interact with a stable environment of pressure p and temperature T0. This environment may be thought of as an infinitely stable, homogeneous surrounding whose temperature, pressure, and composition are virtually unaffected by any process experienced by the system. 5-2 As a preliminary step in the process of deRoversible veloping ari expression that shows the relationWork ship between availability and the state of a system, it is first necessary to prove that a system produces maximum work during a process if it pursues a reversible path. Or, conversely, it would be necessary to prove that,''when work is done on a system* reversible work represents the minimum work required to attain a predetermined end state of the system. Consider a closed system surrounded by an environment at T0 and p0. When the system experiences a differential change from initial state 1 to final state 2, the change in interiM energy dE is independent of the process. Thus for two processes, one reversible and the other irreversible, operating between states 1 and 2, the change in internal energy is a function of only states l a n d 2:

dEr dEi,

where subscripts r and i refer to reversible and irreversible processes, respectively. But according to the first law, the change in internal energy dE is a result of interactions involving
194

Sec, 5-2 Reversible Work / 195

both heat and work, with the environment or,

dE = Q% d\V.
The sum would be identical for reversible and irreversible processes:

dQr + dWr = dQt + dWt.

In a reversible process, th change of entropy is given by dS=pr or dQr = T0dS.

(5.1)

*0
But in an irreversible process, the same entropy change is obtained with a smaller amount of heat supplied: dS>& or dQt <T0 dS.

*0
Hence, since the quantities of heat are different, dQr > dQi, therefore, from Eq. (5.1), the work required is different:

dWr < dW(. (5.2) The work done on a system during a reversible process is less than the work done during an irreversible process even though the same end states are involved in the two processes. In an irreversible process in which work is done on a system, some work must be done in overcoming the dissipative 11-1 Thermodynamic relationships determine the Introduction equilibrium composition of product mixtures resulting from chemical reaction. The nature of the product species, their proportions, their temperature, and their pressure depend upon three major controlling factors. For one thing, the composition of the products of reaction is affected by material balance considerations. This requires that the total quantity of each chemical element in the product mixture be the same as that in the reactants.* We shall therefore consider the calculation of elemental composition of various mixtures and examine the laws of stoichi- ometry which apply in chemical reactions. Second, the resultant temperature and pressure of product mixtures depend upon the first law of thermodynamics. This dictates that the total energy be conserved, just as the total mass is. Hence this chapter gives attention to calculation of flame temperatures of combustible mixtures. Third, equilibrium composition is determined by relationships that arise indirectly from the second law of thermodynamics. The second law dictates that the composition of the products depends on temperature and pressure, whereas the first law indicates that the temperature and pressure of the products depend on their composition. Clearly, then, complex interactions are involved, and problems of calculation of product composition can be handled only by considering both laws simultaneously. Although the principles outlined in this chapter apply to any chemical reaction, particular attention will be given to an important class of chemical reactions, the combustion processes. Combustion may be defined as a rapid exothermic reaction between a fuel and an oxidizer in which chemical energy is liberated. 11-2 Chemical reactions are indicated in a compact Stolchlometry form by means of chemical equations. The and the reaction of carbon monoxide and oxygen, for

Chemical Equation

example, may be written as

CO(g) + * Os(g) 5= COg). (I l.l) The substances at the beginning of the reaction are called reactants, whereas those resulting from the reaction are called products. The arrows indicate the direction of the reaction. At low temperatures, the preceding reaction proceeds from left to right; at high temperatures, the direction is reversed so that C02 tends to dissociate into CO and Oa. The letters in parentheses following each species in Eq. (11.1) identify the phases of the various substances, whether solid, liquid, or gas. The proportions in which molecules of the reactants combine to form This discussion excludes nuclear reactions.

Sec. 11-2 Stoichiometry and the Chemical Equation / 475

the products are also indicated in the chemical equation. In the preceding equation, 1 mole of CO combines with a mole of O, to form 1 mole of C0 2. In abbreviated form, the chemical equation may be written 2 atAt^ S CjCj, (11.2) <=i j-i where at and c, are the relative molal proportions in which the various species At and C} interact. The reactants and products in Eq. (11.2) are identified by subscripts i 1, 2 ... / and j = 1,2 ... k respectively. In a chemical reaction the total mass is conserved, although the total number of moles does not necessarily remain unchanged. Mass proportions are readily obtained from molal proportions by multiplying each component by its molecular weight. In most combustion processes, air serves as the oxidizer. The ratio on a molal basis of nitrogen to oxygen in the atmosphere is approximately 0.7901/0.2099 = 3.76; that is, every mole of oxygen is accompanied by 3.76 moles of nitrogen. On a mass basis, each lbm of oxygen is accompanied by 3.31 lbm (= 0.768/0.232) of atmospheric nitrogen. Although the nitrogen of the air does not contribute to the oxidation reactions, it leaves the reacting system at the same temperature as the products; consequently, its energy, on leaving as a product, is different from the energy it had at the entrance. This factor is taken into consideration in the energy balance of the combustion process. The minimum amount of air required for the complete oxidation of a fuel is called the theoretical or stoichiometric air. The mass ratio of the fuel to the stoichiometric air is called the stoichiometric fuel-air ratio. The stoichiometric form of Eq. (11.2) is vfA, =* 2 VJCJ, (11.3)
-I
J-I

where and v} are called stoichiometric coefficients of the species At and C}. As an example, consider the chemical equation for the stoichiometric reaction of benzene with oxygen: C6H0(/) + 7.5 O2(g) - 6 C02(s) 4- 3 HsO(s). Since each mole of oxygen, in air, is accompanied by 3.76 moles of nitrogen, the complete equation is C0He(/) + 7.5 Os(g) + 7.5(3.76) N2(g) 6 CO,(g) + 3 HsO(g) + 7.5(3.76) Ng),

4/6 / Chap. II Reactive Mixtures

or CaH,(0 + 7.5 O,(g) + 28.2 N,(g) 6 COs(g) + 3 H,0(g) + 28.2 N,(g). The preceding equation indicates that a minimum of 7.5 moles of 02 accompanied by 28.2 moles of Ns are necessary to oxidize completely 1 mole of C6H0 to form 6 moles of C02 and 3 moles of H,0. The amount of air actually supplied may exceed or be less than the theoretical amount required. If excess air is used, oxygen (gaseous) will appear in the products of combustion; if insufficient air is used, the combustion is incomplete and products, such as CO, CH4, H,, and unburned fuel, may also appear. In the previous example, if 20 per cent by volume excess air is supplied, the foregoing equation is written C,H,(/) + 1.2(7.5) 02(g) + 1.2(28.2) N,(g) 6 COt(g) + 3 HjO(g) + 0.2(7.5) 0,(g) + 1.2(28.2) N,(*). In practice, some excess air is generally supplied in order to insure that no unburned fuel is contained in the products. On the other hand, a large amount of excess air is also avoided, because the additional oxygen and nitrogen absorb energy from the system, thus lowering the temperature of the combustion products, and consequently lowering the rate of heat transfer from the combustion products. The fuel used in combustion may be solid, liquid, or gas. Oil and natural gas fuels in common use consist primarily of hydrocarbons. Liquid fuels are often classified in terms of the hydrogen-carbon mass ratio nijmr, whereas natural gas fuels are specified in terms of the mole fractions of their constituents. A fuel often consists of many hydrocarbons, but it is convenient in many cases to express its formula in terms of an equivalent
TABLE

Methane

1 1 . 1 Hydrogen-carbon ratios by atoms for some fuels CH4 4.00

Natural gas Gasoline Kerosene Diesel fuel Heavy fuel oil Bituminous coal Crude oils

3.5 2.1 2.1 1.8 1.5 0.6 1.6 - 1.9

Ethene Ethane Propane Butane Benzene Hexane Heptane Octane Decane Cetane Ethyl alcohol

CJHI C;H QHg C..HI0 CBH0 C6H CrH, o CjH|8 CioH22 CIOH34 C;HcO

2.00 3.00 2.67 2.50 1.00 2.33 2.28 2.25 2.20 2.12 3.00

hydrogen-carbon ratio based on atomic quantities. Table 11.1 lists some fuels and their corresponding hydrogen-carbon ratios. EXAMPLE 11.1: A natural gas has the following composition by volume: Gas Per Cent Methane (CH.,) 67.4 Ethane (C2H6) 16.8 Propane (C3H8) 15.8 Calculate the equivalent hydrogen-carbon ratio for this gas by atoms and mass.

Solution
Composition by Atoms Constituent Mole Fraction CJH 0.674 Carbon 0.674 Hydrogen 2.696

Sec. 11-3 Typical Problems / 47/

0.168 0.336 1.008 0.158 0.474 1.264 Totals 1.000 1.484 4.968 The hydrogen-carbon ratio by atoms is 4.968/1.484 = 3.35 atoms of hydrogen per atom of carbon. The combustion calculations can therefore be based on a hydrocarbon fuel with the chemical formula C|,4 Hi.*. The molal mass of the fuel is 1.484 x 12 + 4.968 x 1 = 22.788 lbm/lb-mole. The hydrogen-carbon ratio by mass is ~ * 1 = 0.279 Ibm of hydrogen/lbm of carbon.
CjHg

CJH8

Wi; 1.4o4 X 1/

11-3 Typical Problems

Problems in stoichiometry are divided into two main categories, depending on whether the composition of the fuel or the composition of

the reaction products is known. EXAMPLE 11.2: Determine the stoichiometric air required for the complete combustion of 1 lbm of normal heptane C7Hm. What is the percentage analysis of the products on a mass and a molal basis? Solution: The chcmical equation is CTH10(/) + 11 0,(*) + 11(3.76) N,(*) - 7 CO,(*) + 8 HsO(|?) + 11(3.76) N,(*). The air-fuel ratio on a mass basis is ~1512 ,bm air/lbm fuel478 I Chap. II Reactive Mixtures Alternately, since there are (11 +11 x 3.76) moles of air, the air-fuel ratio is
(u +

aoo.2o756)X28'97) -15-12 ,bm air/lbm fueL

The air-fuel ratio on a mole basis is 1 1 . .x. = 52,3 moles air/mole fuel. The analyses of the products on a mass and molal basis are as follows: By Mole By Mass co2 7 12.42% 7 x 44 = 308 H2O 8 14.20% 8 x 18 = 144 N2 41.36 73.38% 41.36 X 28 = 1160 Totals 56.36 100.00% 1612

19.11% 8.94% 71.95% 100.00%

EXAMPLE 11.3: Five moles of propane C3H8 are completely burned at atmospheric pressure in the theoretical amount of air. Determine (a) The volume of air used in the combustion process measured at 14.7 psia and 77F. (b) The partial pressure of each constituent of the products. (c) The volumetric analysis of the dry products. Solution: (a) The chemical equation is 5 C3H8te) + 25 0,(g) + 25 (3.76) N2(*) -> 15 C02(*) + 20 H20(^) + 25 (3.76) N20r), or

5 CjHgte) + 25 0.(*) + 94.0 N,(^) 15 C02(*) + 20 H20(^) + 94.0 Nste). Thus, 25 moles of CL are required or 25 (1/0.2099) = 119 moles of air, (25 moles of O., plus 94 moles of N3). If air is assumed a perfect gas, then v = nJtT= 119 >-1545(77 + 460) = 467Q0ftl> p 14.7 x 144 (b) The partial pressures of the product constituents are proportional to the mole fractions. Therefore, p *>> = -f5+-f5--94 x l4-7 = 1-71 Psia> Pa,o = pjj x 14.7 = 2.28 psia,

Sec. 11-3 Typical Problems / 479

Ps. = x 14-7 = 10-71 psia.

Total pressure = 14.7 psia.
(C) V m ~ + W ,

" I5T94

13'7S

. = 1 - 0.1375 = 86.25 per cent. ' COs + ' X EXAMPLE 11.4: The analysis of a sample of coal gives the following values by weight (the remainder is ash). Carbon 80.7% Hydrogen 4-9% Sulfur 1.8% Oxygen 5-3% Nitrogen 1.1% What is the air-fuel ratio by weight if 20 per cent excess air is used in the combustion process? Solution: For 1 lbm of fuel, the following table can be formulated Moles of 0 Required for Complete Combustion Number of Moles of I lbm __ per lbm of Fuel of Fuel Reaction Equation C = 0.0673 0.0673 0.0673 C(s) - 0.0673 Og) - 0.0673 CO,(*)

, 9^2 = 0.0245 0.01225 02(g) - 0.0245 HjO(^)

S 9^8 = 0 000563 02 = 0.001655 0 9^1 - 0.000393 0 0.000563

0.0245 H2(^) 0.01225

0.000563 S(j) - 0.000563 Oo(^) - 0.000563 SO-(^)

_________

O; required = 0.080113 mole 0-> in fuel = 0.001655 mole Difference 0.078458 mole 02 per lbm of fuel Stoichiometric air-fuel ratio = 0.078458(100/20.99) x 28.97 = 10.83 lbm air/lbm fuel. With 20 per cent excess air, the air-fuel ratio is 10.83 x 1.2 13 lbm air/lbm fuel. EXAMPLE 11.5: The composition of a hydrocarbon fuel by mass is 85 per cent carbon, 13 per cent hydrogen, and 2 per cent oxygen. Determine (a) The chemically correct mass of air required for the complete combustion of 1 lbm of fuel. (b) The volumetric analysis of the products of combustion and the dew point if the total pressure is 14.7 psia. (c) If the products of combustion are cooled to 60F, what is the mass of the water vapor that condensed? Solution: (a) Consider the combustion of 1 lbm of fuel composed of 0.85 lbm of carbon, 0.13 lbm of hydrogen, and 0.02 lbm of oxygen. In the complete combustion process the carbon oxidizes to COs and the hydrogen to H20 according to the equations C(s) + Oj(g) * COi(g) Hj(^) + i Ot(g) -* H,OG?). The oxygen requirement as dictated by these two equations is, however, reduced by the amount of oxygen already existing in the fuel. The number of moles of Oj required = ML + = 0.102375 mole of 02/lbm of fuel,
g

^ = 0.07075 + 0.03225 - 0.000625

40U f Chop. II Reactive Mixtures

mass of air = ^2^99^ x 2&.97 = ^.1 lbm air/lbm fuel. (b) The analysis of the products of combustion by mass and volume is given in the accompanying table: lbm per lbm Fuel Moles per lbm Fuel Molal Analysis 007075 COj 3.12 0.136 miH,0 Nj Totals

m* = 0

0645

1.16 10.82 15.1

0.124 0.740 1.000

(3.76 X 0.102375) = 0.385 0.52025

The dew point temperature may be found from steam tables corresponding to the pressure of the water vapor in the combustion products: Pressure of H.O = 0.124 x 14.7 = 1.82 psia. Dew point = 122.5{,F. (c) Since 60'F is below the dew point temperature, some water vapor will condense. The vapor pressure is then equal to the saturation vapor pressure corresponding to 60;F. From steam tables, pc,at at 60F = 0.2563 psia and v = 1206.7 ftJ/lbm. The volume occupied by the water vapor is equal to the volume occupied by the C0 2

Sec. 11-3 Typical Problems / 481

and the N2 at their partial pressure of 14.7 0.2563 = 14.4437 psia. The volume according to the perfect gas law is Y_ nSIT_ (0.07075 + 0.385)1545 X 520 _ , p 14.4437 X 144 Mass of vapor in products = = = 0.1462 lbm. vg 1206.7 Mass of vapor that condensed = 1.16 0.1462 = 1.0138 lbm. EXAMPLE 11.6: A hydrocarbon fuel in the vapor state is burned with atmospheric air at 14.7 psia, 803F, and 60 per cent relative humidity. The volumetric analysis of the dry products of combustion is Product Percentage CO, 10.00 o. 2.37 CO 0.53 Nj 87.10 (by difference from 100) 100.00 Calculate (a) (b) (c) (d) Ratio of hydrogen to carbon by mass for the fuel Air-fuel ratio by mass Air used as percentage of the stoichiomctric value Volume of the humid air supplied per lbm of fuel. Solution: (a) The following table gives the number of atoms of carbon, oxygen, and nitrogen per mole of dry products: Moles (per Mole of Dry Products) Carbon Oxygen Nitrogen CO 0.10 0.10 0.20 o. 0.0237 0.0474 CO 0.0053 0.0053 0.0053 Ns 0.871 1.742 Totals 1.0000 0.1053 0.2527 1.742 Assuming that H20 is the only remaining product of combustion, the amount of hydrogen in the fuel may be determined by finding the amount of oxygen used to form the HtO. Total moles of O. supplied with 0.871 mole of N, = 9^}- 0.231.
3.7 o

Moles of O- accounted for in the reactions considered = 0.12635. Hence the difference used in formation of HsO = 0.10465 moles of Oa. The formation of HsO can thus be expressed as 0.2093 Hs(*) + 0.10465 Os(*) - 0.2093 H20(^), which indicates that 0.2093 mole of HsO is formed per mole of dry products. The hydrogen-carbon ratio in the fuel is 1= Train-3-97 (bJ'atom!)
# weigh,). m^"mmratio =

= = 18.9 lbm air/lbm fuel. 1 .Oo / (c) The number of moles of oxygen required for stoichiometric combustion is 0.1053 CO) +0.1053 02(g) - 0.1053 COj(^) 0.2093 H.(j + 0.10465 Ot(y) -0.2093 H20(i?) 0.20995 moles of 02 per mole of dry products.

482 j Chap. II Reactive Mixtures

Since the oxygen-air ratio is constant in atmospheric air, the percentage of the air supplied is the same as that of the oxygen. Hence the percentage of the stoichiometric air used is 030555 = 1-1 or 110 per cent. (d) The number of moles of dry air is

1 0.87 ^Qjcfj = 1-102 moles air/mole dry products, but the mass of fuel 1.687 lbm fuel/mole dry products. Therefore, the number of moles of air per lbm of fuel 1.102/1.687 =0.653. At 80F PV.SM 0.5069 psia and

pu m 0.6 x 0.5069 = 0.30414 psia.

Hence
T /

n S t T 0.653 x 1545.33 X 540

~ - (14J - 0.30414) X 144 263 ft /,bm f fueL 11-4 The Chemical System and Conservation of Mass
The number of independent properties which define an equilibrium state of a chemical system depends on the number of parameters necessary to define the ambient medium of the system. Two independent properties, such as temperature and pressure, in addition to parameters indicative of the degree of the reaction are sufficient to define the state of a chemical system. The degree of chemical reaction may be indicated by the number of moles of each component, the chemical potential, or by a parameter X called the degree oj advance of the chemical reaction. If the latter is used, an equation defining the state of a chemical system may be written 4>(p, T, X) = 0. (11.4) The advance of the reaction varies from 0(X = 0) at the beginning of a stoichiometric reaction to unity (A, = 1.0) upon termination of the reaction. Thus the advance of the reaction may be defined according to the following equations:

nl = /j? -f- z/i^ n2 = n\ + vtX nr = n + vrX,

or, in terms of the ith component (i = 1, 2 ... r), nt = 4- vtX, (11.5) where nt is the number of moles of component i in the system when the advance of the reaction is X, n is the number of moles of component i at the beginning of the reaction, and vx is the number of moles of component i in the stoichiometric reaction? Summation over all components of the reaction gives I=r i=r lr X nt = n + X vu i=i j=i (-i or

n = n + X Av,
where
(-r
=i

(11.6)
l-r
-I

Imr n = 2 n S nt and Ai/ = 2 iI>I

At the beginning of the reaction, X = 0 and nt = /if. As the reaction progresses, X increases

Sec. 11-4 The Chemical System and Conservation of Mass / 483

continuously until one of the reactants disappears and *The value of vt, as expressed in Eq. (11.5), is positive for products and negative for reactants.

484 / Chap. M Reacf/ve Mixtures

no further reaction takes place. Thus if component 1 disappears first, the maximum value of X of the reaction is given by (n.7)

Vi
The relation between the number of moles of the reactants can be obtained by differentiating Eq. (11.5). Thus the change in the number of moles of any component is given by dnt = Vi dX, (11.8) and accordingly, the proportions of the species created or destroyed have the following relation
= f=
Vy V j Vi

A.

(11.9)

The degree of advance of the reaction X is a function of composition which may be expressed in terms of the number of moles / *, . . . , nT of the components of the system. Therefore at constant temperature and pressure, the differential of a property X = X(p, T, X) with respect to X is !dX\ dnx (3X\ . (dx\ dn 2 . k dnr \dnjp, rdX + " y* W, /p,r w/il/p, T dX But

fdX\ _ , dnt -r = x. and -rr = v,, Kdfii/p'T d\

hence

dX\ ~ ar) XiVy X

OX/p,T

r t

XrvT = "Z XiVi.

i=l

(11.10)

Equation (11.10) expresses the change of a property X with respect to X at constant p and T in terms of the molal properties and the stoichiometric number of moles of the components. Equation (11.5), when multiplied by the molecular weight and summed up for all the components, gives the following equation in terms of the masses of the components: 2 Hi Mi = 2 n\Mt + E vtMiX, 1=1 i.i i=i
or

m = m+tviMi\.

(11.11) i-i Since the mass of the system is conserved during the chemical reaction, that is, m == ?n, it follows that 2 ViMiX = 0. i=i The foregoing equation is also independent of the value of A., hence S vtMt == 0, (11.12) i=] which is a mass balance of the stoichiometric equation (11.3). Note that Eq. (11.12) substantiates the law of conservation of mass applicable to chemical reactions. The foregoing relations were derived for a single reaction of one phase. For several reactions and phases, the procedure is to apply the preceding relations to each reaction and to every phase and to sum up the equations over all the reactions and phases. When phase change occurs as part of the reaction, the energy transfer due to phase change must be taken into consideration. 11-5 To establish an enthalpy scale for elements and Enthalpy of compounds, it is first necessary to choose an Formation arbitrary datum for zero enthalpy. It \yas con ventionally agreed to assign a zero value to the enthalpy of elements in their most stable forms

Sec. 11-5 Enthalpy of Formation j 485

at a standard reference state 'of 1 standard atmospheric pressure and 25C (77F). If an element has two or more stable forms, that form which is stable at 25C is chosen as reference. With this standard reference state established, enthalpies of all species have a common base. The enthalpy offormation* of a compound is defined as the enthalpy change that accompanies the formation of 1 mole of the compound at the standard reference state from elements at the same state. The enthalpy of formation is given the symbol h}, where the subscript f refers to the formation of the compound from its elements, and superscript () indicates that all reactants and products are at the standard state. Thus, if elements A, B, and C at atmospheric pressure and a temperature of 77F combine to form compound AaBCe at the same reference state, then the chemical equation can be written The term heat of formation is often used instead of enthalpy of formation.

486 j Chap. II Reactive Mixtures

aA(g) + bB(g) + cC(g) -* AaBbCc(g). An energy balance gives

+ bhB -f- ch% + r.
TABLE

1 1 . 2 Enthalpy of formation, absolute entropy,

AND GIBBS FREE ENERGY OF FORMATION

(25C (77F) and 1 atm) Substance Symbol

State

ffy kcal*
gm-mole

f
cal gm-mole K 47.997 46.01 36.983 64.34 74.12 73.04 1.3609 37.7611 51.061 47.300 73.95 148.79 54.85 52.45 30.126 102.24 92.83 31.211 49.15 39.19 41.80 44.50 34.948 50.339 45.767 111.55 86.23 49.003 83.40 64.51 59.40 45.106 16.716 40.53

8/ kcal gm-mole 50.000 -3.976 0 30.989 -4.10 17.09 0 160.845 -94.2598 -32.8077 -15.3 11.98 -7.860 16.282 0 1.94 -0.07 0 -7.892 0 7.59 -12.140 0 20.719 0 3.95 1.58 0 -2.00 -5.614 -71.79 -54.6351 -56.6899 0

Acetylene Ammonia Argon Benzene n-Butane 1-Butene Carbon Carbon dioxide Carbon monoxide Carbon tetrachloride n-Dodecane Ethane Ethylene Helium n-Heptane n-Hexane Hydrogen Hydrogen sulfide Krypton Mercury Methane Neon Nitric oxide Nitrogen n-Octane Oxygen n-Pentane Propane Sulfur dioxide Water Xenon

C,H2

NHj A CH QH10 C<H8 c co2 CO CCI4 C12H28 C,H6 C1H4 He CTHIO QHU Hj H.S Kr Hg
CH4

Ne NO N,
C8H18

02 CaH,s CjHe SOi HjO Xe

Gas Gas Gas Gas Gas Gas Graphite Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Liquid Gas Gas Gas Gas Gas Liquid Gas

54.194 -11.04 0 19.820 -30.15 -0.03 0 171.698 -94.0518 -26.4157 -25.5 -69.52 -20.236 12.496 0 -44.89 -39.96 0 -4.815 0 14.54 -17.889 0 21.600 0 -49.82 -59.74 0 -35.00 -24.820 -70.96 -57.7979 -68.3174 0

*1 cal/gm-mole = 1.8 Btu/lb-mole; 1 cal/gm-mole K = 1 Btu/lb-mole R. SOURCE: Data from National Bureau of Standards Circ. 500, February, 1952, and from API Research Project 44, National Bureau of Standards, Washington, December, 1952, as adapted by E. F. Obert, Concepts of Thermodynamics, McGraw-Hill Book Company, 1960. where AApr, is the enthalpy change at the standard reference state per mole of products. By definition, fi0B, and hi are zero, and therefore, the enthalpy of formation is equal to the enthalpy of the compound at the standard reference state, or

Sec. 11-6 Enthalpy and Internal Energy of Reaction / 487

A positive value of ft means that the enthalpy of formation of the compound is more than the enthalpy of its elements at the reference state. Such compounds are often unstable. A compound at a temperature T above 77F will then have an enthalpy equal to the sum of its enthalpy of formation plus the sensible enthalpy above the standard state, or h = h) + (hT - hs). , (11.13) Table 11.2 gives enthalpies of formation for a number of substances. The table also shows values of absolute entropy and Gibbs function of formation discussed in Section 11.12. 11-6 Chemical energy is part of the internal energy Enthalpy and of a system and is attributed to the binding Internal energy between the atoms of the substance. In Energy of. previous chapters, chemical reactions were not Reaction considered, and consequently, chemical energy was excluded. In this chapter, however, chemical energy constitutes the major part of the internal energy term in the first law. In chemical reactions, one important concern is the amount of heat transfer due to the reaction. Two cases will be considered: (1) when the reaction takes place at constant pressure, (2) when it takes place at constant volume. Consider first, the constant-pressure process. If no work other than reversible work is done, the first law of thermodynamics applied to a closed system is The differential of the enthalpy H H(p, T, X) is Substituting in the first law and letting dp 0 for a constant-pressure process, yields

(JQ = dH V dp.

488 I Chap. II Reactive Mixtures The coefficient of dT, where Cp is the specific heat per mole at constant pressure. The coefficient of dX, (dH/dX)p T is called the enthalpy of reaction and is given the symbol AHPtT. It is equal to the amount of heat interaction when the reaction is carried out at constant pressure with no change in temperature. Therefore, dQp = (rtdp)a dT + A//pr dX. Integrating the foregoing equation between a reference state (o) and any other state, gives QP = J (ncp)x dT + J AHVtT dX. (11.14) If the reaction is stoichiometric where X changes from 0 to 1, and if, further, the temperature at the end of the reaction is equal to the temperature at the beginning of the reaction, then Qp = f A HT dX = A HPiT, (11.15) J0 which means that the heat interaction is equal to the enthalpy of reaction subject to the conditions previously stated. According to Eq. (11.10), A//p,t = = 2 Viht = (2 vtA,)p - (2 ViR%)n (11.16)

\OA/p,r t

where subscripts r .and p on the right-hand side of Hq. (11.16) refer to reactants and products,

respectively. In the case of exothermic1 reaction, AHVT is negative and (2 "ii*i)P < (2 vt&di- < i Similarly, if Hp T is positive, the reaction is endothermic and (2 vtht)p> (2 vihi),. 1 I The second case to be considered is the constant-volume process. The procedure is analogous to the constant-pressure case. The first law applied to a closed system when only reversible work is involved is dQ dll + p dV. The differential of U = i/(V, T, X) is Substituting for dU in the first law and considering constant volume, then

where (dU/dT)r,x cv being the specific heat per mole at constant volume, and (dUld\)y T = A UV T is called the internal energy of the reaction. Therefore,

&Qv = (ncu)x dT + A Ur>T dX,

where AUr T, according to Eq. (11.10), is given by
AC/,-.r =
\o\/r.T i

(11.17)

= S Wi = (E vtut), ( VtiiJr.
i i

(11.18)

The relation between A//p r and AC/KiT is obtained as follows:

AH'T = [2 vi(itt +PiWt)]p [2 vt{u{ + AVi)]r i i
= it =

(2 Mi)r] + [2 V l P i V ,]p [2 I I At/,-ir + [2 V l P l V t ) p [2 VtPiVilr( I

ViU^f

[(2

VlPiVl]r

In the case of reactions involving liquids and solids, the changes in volume are small and can be neglected in comparison to gaseous substances in the reaction. If, further, the gaseous reactants and products are considered perfect gases, then ptvt 8%T. Therefore, ( Note that the term in parentheses is the change in the number of moles due to the reaction. Therefore, AHp T = AC/K-r if there is no change in the number of moles of the gaseous substances due to the reaction.
AHp T = At/F r + @T 2 (ylf - vlt). (11.19)

1A reaction in which heat interaction is negative is called exothermic; a reaction in which heat interaction is positive is called endothermic.

Sec. 11-7 Enthalpy of Reaction at the Standard State / 489 T A B L E t i . 3 Enthalpy of combustion (AH at 77F)

EXAMPLE 11.7:

The chemical equation for n-octane when burned with oxygen at 77F

is QH18 (/) + 12.5 0,(*) - 8 CO. (g) + 9 HtO(*). If the enthalpy of reaction at constant pressure AHPtT = 19,256 Btu/lbm, calculate the internal energy of reaction. Assume all gases to be perfect. Solution: Neglecting the volume occupied by liquid octane, the change of number of moles is Vi = (9 + 8) - 12.5 = 4.5 moles. Using Eq. (11.19), AUV.T = - T(A.5) icm< 1-986 x 537 x 4.5

-19256

= -19256 -43 = -19299 Btu/lbm.

11-7 The change of enthalpy in a chemical reaction Enthalpy of depends only on the initial and final states of Reaction at the the system. The difference between the energy Standard State of the reactants and products
is equal to the energy released during the reaction. As mentioned in Section 11-5, a standard state (p = 1 atm, T = 537R) is chosen as a basis for comparison. A more appropriate standard state would be at 0R, but difficulties in measurement at or near such temperature have excluded this possibility. The enthalpy of the reaction at the standard state is equal to the difference between the enthalpies of the rcactants and products measured at the standard state, or AH = (X Vi^)p - (!>,?),. (11.20)
i I

Thus AH is in effect a comparison between the enthalpies of the reactants and products at the standard state. A negative sign in front of AH means that the enthalpy of the products is less than that of the reactants (exothermic reaction) which is typical in combustion processes. Table 11.3 gives enthalpies of combustion of some hydrocarbon fuels. The enthalpy of reaction can, in many cases, be measured by direct calorimetry. It may also be calculated from the enthalpies of formation according to the equation A H = (Hr\ - (#?),, (11.21) which states that the enthalpy of reaction AH is equal to the difference between the enthalpies of formation of all the products and all the reactants. Enthalpy of Vaporization HQ(/) and COs(g) H.Q(g) and COs(g) Substance Symbol kcal Btu kcal Btu h/g, gm-mole lbm (Btu/lbm) gm-mole lbm Acetylene QHjte) 310.62 21,460 300.10 20,734 Benzene CH0(*) 186 789.08 18,172 757.52 17,446 n-Butane C4H,ote) 156 687.65 21,283 635.05 19,655 Isobutane CjHio(f) 141 685.65 21,221 633.05 19,593 1-Butene 156 649.45 20,824 607.37 19,475 C4Hs(g) Carbon C(graphite) 94.0518 14,086 Carbon monoxide CO(g) 67.6361 4,343.6 n-Decane C.oHjji^) 155 1632.34 20,638 1516.63 10,175 n-Dodecane C,jHMte) 155 1947.23 20,564 1810.48 19,120 Ethane C;H#(^) 372.82 22,304 341.26 20,416

490 j Chap. II Reactive Mixtures

(Reactants)^

Ethylene C.H4(*) 337.23 21,625 316.20 20,276 n-Heptane CTH,6(^) 157 1160.01 20,825 1075.85 19,314 n-Hexane C6Hi4(*) 157 1002.57 20,928 928.93 19,391 Hydrogen H,(f) 68.3174 60,957 57.7979 51,571 Methane CH4(i) 212.80 23,861 191.76 21,502 n-Nonane CH2ate) 156 1474.90 20,687 1369.70 19,211 n-Octane 156 1317.45 20,747 1222.77 19,256 cjttMi n-Pentane 157 845.16 21,072 782.04 19,499 C5H Jg) Isopentane 147 843.24 21,025 780.12 19,451 cMg) Propane C,Ha<*) 147 530.6 21,646 488.53 19,929 Propylane 491.99 21,032 460.43 " 19,683 CjHo(g) SOURCE: Data-from API Research Project 44, National Bureau of Standards, Washington, December, 1952, as adapted by E. F. Obert, Concepts of Thermodynamics, McGrawHill Book Company, 1960. At any temperature T, other than the standard temperature (7 = 537R), the enthalpy of reaction AHr depends on the temperature of the reaction. Consider the change of state of a chemical system at atmospheric pressure from state 1 to state 2; first along path a and second along paths i't c, and d as shown in Fig. 11.1. States 1 and 2 are at Ta = 537R and 3

(Products^

% AH Fig. 11.1. Evaluation of AHT at a temperature other than T.

T

fjw8!
(Reoctonts) and 4 are at temperature T. The process along path a is the conversion of the reactants to products at a temperature 537R. The enthalpy of reaction is A# and may be computed from Eq. (11.21). Since the change of enthalpy is independent of the path, the same result may be obtained by changing the state of the system from state 1 to state 2 along paths b, c, and d. The changes of enthalpies along these processes are given by ( J ' A Hr and ( E .i* dT^. Hence AHT = SfaBfa - s (nth,)r] i i = E (ih/,-r Jr n(cPldTj 'z(nth/l + J ntCPldT
(11.22)

A term in common usage in combustion processes is the heating value of a fuel. It is equal to the enthalpy of combustion but of opposite sign. The heating value is a positive number. There are two types of heating values, depending on the phase of the

Sec. 11-7 Enthalpy of Reaction at the Standard State / 491 T A B L E t i . 3 Enthalpy of combustion (AH at 77F)

water formed in the products of combustion. The higher heating value (HHV) is measured when all the water vapor is condensed at the reference temperature T0. If the water is in the vapor state, the lower heating value (LHV) is measured. The relation between these two values is LHV = HHV - m:0h% = HHV - (1050.4)ir.mHlO, (11.23) where m,lt0 is the mass of the water vapor in the products per lbm of fuel and the heating values are in Btu/lbm of fuel. EXAMPLE 11.8: Find the heat interaction when propane C 3H3fe) is burned according to the chcmical equation C,H8(s) + 5 0,{g) -> 3 CO.(*) + 4 H,0(/). Assume both reactants and products are at a pressure of 1 atm and 77*F. All gaseous components follow the perfect gas law.

Solution: The enthalpies of formation for the reactants and products are (Hs)r = (h/)c,u.
+ 5 {h})0l = -44,676 + 0 = -44,676 Btu,

Sec; 11-7 Enthalpy of Reaction at the Standard State / 49C (H,)p = 3 (h0,)co, + 4 {ft})h,o = 3(-169,293) -I- 4(-122,971) = -999,762 Btu.

The heat interaction in this case is equal to the difference between the enthalpy oi formation of the products and reactants, and is given by , Atf = Qpr. = {H}\ - {H% m -999,762 - (-44,676) = 955,087 Btu/lb-mole of propane. EXAMPLE 11.9: Calculate the enthalpy of reaction at the standard state of benzene C6H6 when it reacts with oxygen at 77F to form carbon dioxide and liquid water. Solution: C8H0(/) + 7.5 02(^) -* 6 C02{g) + 3 HjO(/). The enthalpies of formation of the different species, according to Table 11.2, are
(tf/)c,H. = 35,630

Btu/lb-mole m o, = o

= -169,293 Btu/lb-mole (//?),o = -122,971 Btu/lb-mole. Therefore, A// = 2 H)p - /)r = [6(-169,293) + 3(122,971)] - [35,630]
= -1,420,291 Btu/lb-mole of C,H6.
EXAMPLE 11.10: Calculate the enthalpy of formation of n-heptane if the enthalpy of combustion is AH = 1160.01 kcal/gm-mole. Solution: The combustion equation is

CTH10te) + 11 Oate) - 7 C0.2te) + 8 HsO(/) kcal/gm-mole. Atf = -1160.01 = lh}CQt + 8|i0 = 7(94.0518) + 8(68.3174) - h}0 H ...

= -1160.01

From which ^ = 44.8918 kcal/gm-mole, which agrees with the value given in Table 11.2.
EXAMPLE 11.11: The enthalpy of combustion of n-octane.when the water formed in the products is in the liquid phase is 20,747 Btu/lbm (Table 11.3). What is the value of the enthalpy of combustion if the water in the products remains in the vapor phase? Solution: The combustion equation is CbH1&<>) + 12.5 Og) -* 8 CO,Qr) + 9 H,0(/) AH0 = -20,747 Btu/lbm. The difference between the two values of enthalpies of combustion per lbm of fuel is equal to the amount of H20 formed per lbm of fuel multiplied by its enthalpy of vaporization.

mass of H20 = 8 xff+igffi TT3 " 1,42 lbm/Ibm of fuel Therefore,

-AH with H2Ofe) = 20,747 - 1.42 (1050.4)7T.F

= 20,747 - 1,490 = 19,257 Btu/lbm. This checks with the value given in Table 11.3. 11-B With the preceding definition of the standard First Law state, the enthalpy of formation, and enthalpy Applied to of reaction, the first law may be expressed in Chemical the form of Eq. (3.49) as

Reactions

Sec. 11-9 Adiabatic Reaction Temperature / 495

[2 - K)]r + Q + W + (-A H ) = [2 v t (h t - hl] p , (11.24) and on a mass basis [S m^hi - hl)]r + Q + W + (-AH) = [S mt(ht - A?)]p. (11.25) Gas tables* which take variations of specific heats into consideration may be conveniently used to determine the enthalpies of the species, as the following example illustrates. EXAMPLE 11.12: One lbm of C7H|8(^) at 77F is burned with 100 percent excess air at 120F in a constant-pressure steady-flow process. If the products of combustion leave at 700F, determine the amount of heat transferred. Solution: The chemical equation of the reaction is CjUM + 2(11) Os(*) + 2(11 x 3.76) N,(*) - 7 C02Q>) + 8 H,0(*)
+ 2(11 X 3.76) N2(i) + 11 02(^),

*J. H. Keenan and J. Kaye, Gas Tables, New York: John Wiley & Sons. Inc., 1948. C7HI6Qr) + 22 0,(*) + 82.72 N,(*) - 7 CO^g) + 8 HaO(*) + 82.72 N2(^) + 11 Os(*). Neglecting changes in kinetic and potential energy, the amount of heat transferred to the chemical system is given by the first law, according to the relation Q = Hp - Hr.
Hr (A/)c.i(a)

+ 22(/. - h77)o, + 82.72(htso- A)x,

= -80,900 + 22(4027 - 3725)0, + 82.72(4028 - 3730)X| = -80,900 + 6640 + 24,650 = -49,610 Btu/lb-mole of fuel.

Hv 7(A/ + ft TOO ft 7r)cot + 8(A/ 4- AT00 A77)h,o

+ 82.72(/Ttoo h77)s. 4- 11 (A too ^-7)0, = 7(169,293 + 10,490 - 4030) + 8(-104,071 + 9467 - 4258) + 82.72(8129 - 3725) + 11(8314 - 3730) = 1,516,303 Btu/lb-mole of fuel. Hp can also be calculated from Keenan and Kaye, Gas Tables (Table 7) as

Hp = 7(-169,293) + 8(-104,071) + (7 + 8 + 82.72 + ll)(A-00 - K)p = -1,185,051 - 832,568

+ 108.72(8375 - 3774) = 1,517,619 Btu/lb-mole of fuel. Therefore, Q = 1,516,303 +49,610 = 1,466,693 Btu/lb-mole of fuel. 11-9 Under adiabatic conditions, the temperature Adiabatic attained in a reaction is called the adiabatic reReaction action (or flame) temperature. In actual proTemperature cesses the combustion temperature is considerably less, owing to the inevitable heat interaction with the environment. Also, some of the reactants may fail to react, or may decompose only partially. Dissociation of the products of combustion also results in a further reduction of the combustion temperature. The adiabatic reaction temperature is an upper limit of temperature and therefore is a useful parameter in the design of combustion chambers. The adiabatic reaction temperature may be determined from the first law which reduces to E HT = Hv. (11.2 6) The following example illustrates the use of Eq. (11.26). EXAMPLE 11.13: Calculate the adiabatic reaction temperature of QHu^) when

496 j Chap. II Reactive Mixtures

burned with 100 per cent excess air at atmospheric pressure. Assume no dissociation and the reactants to be at 77F. Solution: The chemical equation is CTHie(*)+ 22 Og) + 82.72 N,(*) ->7 COs(*) + 8 H,0(*) + 82.72 Nj(tf) + 11 O t(g). Several methods of solving this problem will be presented. The adiabatic reaction temperature will be computed, making use of (a) gas tables for 200 per cent theoretical air; (b) enthalpy of formation; (c) enthalpy of combustion; (d) specific heat equations. (a) 2 HT = AH = 19,314 Btu/lbm of fuel = 19,314 x 100 = 1,931,400 Btu/lb-mole of fuel 2 Hp = [2 (wt^t)r 2 (w(A)tt]p*
T l

Therefore, 1, 931,400 = (7 + -8 + 82.72 + ll)(/ir - h17).

But from Table 7 of the gas tables, at 77F, h = 3774 Btu/lb-mole of products. Therefore,

hT = 3774 + ^sSIt - 3774 + 17,770 -- 21,544 Btu/lb-mole of fuel.

From gas tables, the temperature corresponding to this value of f\T is Tprwiucu 2728R. (b) If enthalpies of formation are used, then 2 Hr = (ft})o,n,.(<7) = 80,900 Btu/lb-mole of fuel

Hp = l{h} + hr h77)co, + 8 (h} + hT h77)lt, 0 + 82.72(Ar h77)s, + 1 l(hT fi77)o,

= 7(-169,293 + itTa0i - 4030) + 8( 104,071 + rIIf0 - 4258) + 82.72(ArVj - 3736) + ll(/r0l -3725). Assuming T = 2728R as found in part (a), gives

2 H = 7(30,973 - 173,323) + 8(25,272 - 108,329)

+ 82.72(20,480 - 3,736) + 11(21,428 - 3,725) = 2827 Btu/lb-mole of fuel as compared to 80,900. Assume T = 2700R 2^, = 7(30,581 - 173,323) + 8(24,957 - 108,329) + 82.72(20,246 - 3,736) + 11(21,183 - 3,725) = 108,132 as compared to 80,900. Assume T = 2710R 2 Hp 7(30,721 - 173,323) + 8(25,070 - 108,329) + 82.72(20,430 - 3,736) 4- 11(21,270 - 3,725) = -91,281 Btu/lb-mole of fuel. From the preceding trials, a good approximation of T is 2712R. (c) If the enthalpy of combustion is used, then Xifr = AH = 19,314 Btu/lbm of fuel = 19,314 x 100 = 1,931,400 Btu/lb-mole of fuel.
2 Mp ~ 7(Aj A77)(;0l %(hT h17)ul0 + 82.72(hr

Sec. 11-9 Adiabatic Reaction Temperature / 497

+ 1 l(^r Att)os-

Assuming a temperature T = 2710R gives 2

Hp = 7(30,721 - 4,030) + 8(25,070 - 4,258)

+ 82.72(20,430 - 3,736) + 11(21,270 - 3,736) = 186,837 + 166,496 + 1,380,000 + 192,995 = 1,906,328 Btu/lb-mole of fuel as compared to 1,931,400. Note that this method utilizes the enthalpy of combustion as compared to method (b) where the enthalpies of formation are used. The relation between these enthalpies, according to Eq. (11.21), is clearly
A

H m (AH% - 2 (AH})r

or -1,931,400 = [7(169,293) + 8(104,071;] - [-80,900]. The slight difference between the two sides of the previous equation is due to different sources of enthalpies of combustion and of formation. Method (c), therefore, should give the same result as method (b), that is, T = 2712R. (d) If the constant-pressure specific heat equations are used, then 2 Hr= -AH = 1,931,400 Btu/lb-mole of fuel. 2 Hp = 7 ePM' dT m 8 cPiW dT + 82.72 i,5f dT

498 j Chap. II Reactive Mixtures

Substituting for the values of cp (Table A.3, Appendix) gives

Assuming values of T, 2 can be evaluated and should be equal to 2 Hr at the correct T. This calculation leads to a value of T not much different from those determined by the previous methods. (The check is left to the student as an exercise.)

11-10 Second Law Applied to Chemical Reactions

The second law of thermodynamics dictates that the entropy of an isolated system can never decrease; it may increase or remain unchanged. The equilibrium composition of an isolated system corresponds to the state of maximum entropy subject to the imposed constraints on the variation of the system. Therefore, as explained in Chapter 5, entropy can be used as a criterion of equilibrium for an isolated system. Chemical reactions generally take place while the system is in contact with an enivronment at constant pressure and temperature. Furthermore, chemical reactions are not restricted to isolated systems. Therefore, entropy is not a readily applicable criterion to determine equilibrium compositions under these conditions. The Gibbs function (free energy) fills this gap and may be used to predict the spontaneity of chemical processes as well as their equilibrium compositions. As explained in Chapter 5, the spontaneity of a chemical reaction at constant temperature and pressure is associated with a decrease in the Gibbs function such that
(11.27) (11.28)
(dG) p .r=
(AG)PiT - (C, - Gt)p,r < 0 .

The equilibrium state corresponds to a minimum value of Gibbs function, so that

0.

Another criterion of equilibrium in a chemical system is given in terms of the chemical potential. At constant temperature and pressure, the differential of the Gibbs function according to Eq. (5.57) is dGpT = E p.t dnu where /Z, represents the chemical potential and nt represents the number of moles of the ith species. But from Eq. (11.9)

dnt dn.,

Vi
where subscript 1 refers to component 1. Therefore dGPtT = E Li'^-dnx.

Sec. 11-11 Chemical Affinity / 499

At equilibrium, since dGpT = 0, and since vx and dnx are not zero, therefore E = 0. (11.29) Equation (11.29) presents the criterion for chemical equilibrium in terms of the chemical potential and the' number of moles of the species inThe system. The negative of E vtp-t's called the affinity of the reaction. Affinity is discussed in more detail in the following section. 11-11 Tn a reversible process in which p-V work is Chemical the only work involved, the energy relationships, Affinity according to the first law of thermodynamics, are as follows: dQ = dH V dp. Since enthalpy is a function of temperature, pressure, and the extent of the reaction X, enthalpy may be expressed in the form:

(f L *+( f
Each of the three coefficients of this equation can be described with equivalent terms:

Therefore enthalpy can be expressed as

dH = (Mp)xdT + V-T
By using this expression for enthalpy, the first law then becomes
(11.30)

<?Q = (nS)A d T - T ^ dp + AH9tT dX.

The rate at which a reaction proceeds depends upon the concentration of the reactants. During the course of a reaction, the concentration of reactants ordinarily decreases, so that the rate of reaction constantly diminishes. Finally, when equilibrium is reached the affinity of the reaction is zero and the reaction stops completely. In an irreversible process, the entropy change and the heat transfer are related through the inequality

Td S > dQ.
If dQ' represents the heat required in excess of that used if the process were reversible, then the preceding inequality can be replaced by an equality, *To obtain this equivalent expression, the first and second laws are first combined in the form clH = TdS 4-

V dp.
Consequently as follows: But according to the Maxwell relation The change of enthalpy as a function of pressure, at constant temperature, is

T dS dQ + dQ'. (11.31) Thus if dQ/T represents the entropy increase due to the reversible portions of a process, then dQ'fT represents the entropy increase due to the irreversibilities of the process. The amount of heat dQ' in an irreversible reaction is associated with the extent of the reaction. The ratio of the differentials of these terms expresses the affinity of a system,

500 j Chap. II Reactive Mixtures

Miff

MR

The entropy change can now be expressed, through Eq. (11.31), in terms of affinity: T d S = d Q + zdX. In Eq. (11.30) the heat interaction is expressed as a function of temperature, pressure, and extent of reaction. Entropy and affinity can therefore be introduced into this equation so that dS = - jg|^ ^ dp + dX. Since entropy is a property which can be determined by temperature, pressure, and X, it can be expressed as The coefficients associated with the extent of the reaction in the preceding two equations can be equated: dS\ m &H..T + z _ d X J p , r T From which But it was shown previously in Eq. (11.10) that entropy and X are related as follows:
= M Vi Si (Sp ~ Sr)p,T \0MptT t- 1

Therefore affinity can be described by z = -AHP'T + T A S p r = -AGPi, = -2 */*,, (1134) where ASPiT is the difference in entropy between the products and the reactants when they are at the same pressure and temperature. Evidently affinity indicates the decrease in Gibbs function that occurs during chemical reaction. When a system is in equilibrium the Gibbs function is zero, and so there is no chemical affinity. 11-12 During the course of a chemical reaction, many Free Energy intermediate compositions are formed before and Chemical equilibrium is reached and the final composition Equilibrium is attained. In a chemical reaction, the products can react in the reverse direction, forming reactants, just as the reactants form products in the forward direction. At equilibrium, the rates of the forward reaction and the reverse reaction are equal. In this section the factors governing the final composition of a chemical system are considered. The Gibbs function is the main criterion for equilibrium. The reference state for the Gibbs free energy of formation is 77F and 1 standard atm. The stable form of each element at the standard reference state is arbitrarily assigned a value of zero free energy of formation. The free energy change of any reaction is given by AG = S(G?)p-2(<?/)r. (11.35) When a compound is formed from its elements, the resultant free-energy change at the standard state represents the standard free energy of formation G} of the compound. A negative value of AG indicates that reactants at the standard state proceed spontaneously to products at the standard state. Conversely a positive value of AG indicates the reaction does not take place spontaneously. Table 11.2 gives the free energy of formation of several substances. The free energy change of a chemical reaction under isothermal standard-state conditions may be determined according to the equation A G = A H T0 A S. (11.36) The change of entropy AS is determined from the absolute entropies of the reactants and products at the standard state according to the equation AS - 2 S - s 5?. (11.37)

Sec. 11-12 Free Energy and Chemical Equilibrium / 501

Absolute values of entropy of several pure substances at the standard state (77F and 1 atm pressure) are listed in the Table 11.2. According to the third law of thermodynamics, the entropy of a pure substance in equilibrium approaches zero as the temperature approaches zero. Thus a datum point for entropy is established at zero absolute temperature. Note that elements as well as compounds have entropies greater than zero at 77F and 1 atm pressure. At other temperatures and pressures, the absolute entropy of a perfect gas can be calculated from the Sackur-Tetrode equation which developed from statistical mechanics. When the entropy of a perfect gas is known at one pressure and temperature, its entropy at another set of temperature and pressure conditions can be calculated from
(11.38)
s = J + Cp In St In S-.

o * 0

Po Po

As in the case of enthalpy of formation, the difference between the entropy of a compound at the standard state and the entropy of its elements at the standard state is the entropy of formation:

AS} = S
(11.39) The standard state is 77F and 1 atm pressure. The Gibbs function can be expressed as dG = dH TdS - S dT. But it was shown that entropy could be expressed in terms of reversible heat interaction and affinity:

T dS = dQ + z d\.
From the first law of thermodynamics, this becomes

TdS = d H - V d p + zd\.
Therefore the Gibbs function becomes

dG = - S d T + V d p - z d \ .

(11.40) Since the Gibbs function is a property determined by temperature, pressure, and extent of reaction,