THERMOCHEMISTRY (First Law of Thermodynamics) I. TERMS AND DEFINITIONS A. Definitions 1.

Thermodynamics = Study of the exchange of heat, energy and work between a system and its surroundings. a. System = That part of universe of interest. (reaction vessel, etc.) b. Surroundings = Rest of universe. c. Some types of systems. 1) Open systems = Mass, heat, energy and work can be exchanged. These are important to engineers in flow systems 2) Closed systems = No mass can be exchanged, only heat, energy and work. These are usually encountered in the laboratory 3) Isolated system = No mass, heat or work can be exchanged. The universe is an example of an isolated system. d. Exchange takes place at boundary between system and surroundings during a change in state of system. 1) State = That condition in which all variables are fixed and unvarying. 2) When one or more of these variables are changed, the system changes state. 3) Examples: Temperature Changes Gas at V1, P1, T1 -----------> Gas at V2,P2, T2 ( PV = nRT is the equation of state for an ideal gas ) Phase changes ( solid ----> liquid; liquid ---> gas: etc. ) Reactants ----------> Products 2. Can control some variables or conditions during a change. a. Isothermal Change = One at constant temperature (supply or take away just enough heat so that the temperature remains constant). b. Adiabatic Change = No heat is exchanged during change, that is, the system

is insulated from its surroundings. c. Isobaric Change = One at constant pressure. d. Normal laboratory conditions are isothermal and isobaric ones. B. State Functions ( or State Variables ). 1. Variables (properties) whose value depends only on the state of the system. a. Define the state. b. Value does not depend on the past history of the system. c. Examples: State functions -------- T, P, V, Energy. Not State functions --- work(W), heat change(q) 2. Thermodynamics is concerned with how the state variables change during a change of state. It views these changes in the light of three laws. Recall that in science a law is simply a summary of experience. C. Work (W ) 1. Sense of W. W is positive when work is done on the system by the surroundings. When the system does work, W is negative; the system has to expend energy. 2. Some types of work. a. Mechanical work - exert a force through a distance. W = ( force )x( distance ) or W = f(x)

If force is not constant, W = f dx b. Work of expansion of a gas under constant pressure. (PV work) Consider the work done when a gas in a cylinder, fitted with a weightless, frictionless piston of area A, is expanded under a constant pressure P by moving the piston from position l1 to l2.

l2 Pressure = (force)/(area) or W = f(l) = f(l2 - l1) A l1 P = f/A but f = PA

At constant P, W = PA(l2 - l1) = P(A l2 - A l1) = P(V2 - V1) = PV Note if V2 > V1, W is and the system does work, the work of expansion c. Electrical work. W = (charge)x(voltage) = (coulombs)x(joule / coulomb) = joule 3. Dimension conversion. a. Because of the different formulas for calculating work, a number of different units for work can be obtained. They should be converted to the usual SI unit of joules (kg m2/s2). This can be easily done using the Gas Constant, R, which has a general dimension of

Energy . mol K

Example. A gas is expanded from a volume of 5.00 L to 9.00 L under a constant pressure of 2.00 atm. Calculate the work done on expansion in joules. W = PV = P(V2 - V1 ) P = 2.00 atm What is the work in joules? W = ( 8.00 L atm ) C. Heat (q). 1. Sense of q.
8.314 J/molK = 811 J 0.08206 L atm/mol K

V2 = 9.00 L

V1 = 5.00 L

W = (2.00 atm )( 9.00 L - 5.00 L ) = 8.00 L atm

a. q is positive if heat energy is absorbed by the system (flow into the system) b. q is negative if heat is evolved by the system (flows out of the system). 2. The value of q can be measured experimentally in calorimetry. Calorimetry 1. Calorimeter = Instrument used to measure heat changes (q) in a reaction. a. Calorimeters can be operated either under constant pressure (isobaric) conditions, (Constant Pressure Calorimetry) or at constant volume (Constant Volume or Bomb Calorimetry). b. In both cases the reaction vessels in commercial calorimeters are surrounded by a measured amount water at a particular temperature. The heat lost or gained during the reaction under study (qRXN) will be transferred to the calorometer (qcal) and change the temperature of the water. Since the calorimeter is completely insulated, qtotal= 0 = qRXN + qcal (the calorimeter is an Adiabatic instrument) . By measuring the temperature change (t) caused by the reaction, the heat change (qcal ) can be determined from the following relationship: qcal = C(t). C = the heat capacity of the calorimeter in joule/, q is the heat in joule and t is in (either Celsius or Kelvin). c. The value of C can be obtained by calibrating the calorimeter. This is done by running a reaction whose value of q, is known to a high degree of precision and measuring the temperature rise (tcal), and calculating C=
q cal . !t cal

If the amount of water in the calorimeter is always the same and care is taken to make measurements under the same conditions, the heat capacity of the calorimeter, C, will be the same. d. Once C has been determined, it can be used to calculate qs for other reactions from the measured ts and the relationship q = C(t). Example. The heat of combustion of benzoic acid (C7H6O2) is equal to 26.434 kJ/g. In a calibration run of a bomb calorimeter, it was found that the combustion of 0.530 g of benzoic acid raised the temperature of the calorimeter by 3.47 C. Under equivalent conditions, the combustion of 0.463 g of cyclohexane (C6H12) raised the temperature of

the calorimeter 5.34 C. Calculate the heat capacity of the calorimeter and the heat of combustion of cyclohexane in kJ/mol. 1) Calibration, heat capacity of the calorimeter, C: The heat of combustion of benzoic acid = 26.434 kJ/g, the negative sign means that 26.434 kJ of heat is evolved (given off) when 1.00 g of C7H6O2 is burned; this is the heat absorbed by the calorimeter.. Heat change of the calorimeter = qcal = q RXN = (0.530 g)(26.434 kJ/g) = 14.01 kJ tcal = 3.47 C. Therefore, 14.01 kJ = C (3.47 ) C=

14.01 kJ = 4.04 kJ/ = Heat capacity of the Calorimeter 3.47

2) Heat of Combustion of C6H12 (MM = 84.2) Heat of reaction = qRXN = qcal = (4.04 kJ/)(5.34 ) = 21.56 kJ mol C6H12 reacted =

0.463 g = 5.50 x10 3 mol 84.2 g/mol

Heat of combustion kJ/mol =

21.56 kJ = 3.92x103 kJ/mol 3 5.50x10 mol

II. THE FIRST LAW OF THERMODYNAMICS A. Statement of the first law. 1. Law of Conservation of Energy. The total energy of the universe (or any isolated) system is constant. Energy can neither be created nor destroyed but can be converted from one form to another. a. Example. When an object is dropped from a height, the following energy changes take place. Gravitational Potential Energy (PE) ---> Kinetic Energy (KE) ---> Heat Energy Example. Suppose a 500 g block of Cu is dropped from a height of 300 m. Assuming that the acceleration of gravity , g = 9.8 m / s2 and that air friction can be neglected, calculate: 1. the PE at the start. PE = Gravitational Potential Energy = g m h where m = mass in kg, h = height in meters PE = ( 9.8 m / s2)( 0.500 kg )( 300 m ) = 1.47x103 J 5

2. the KE on impact. KE = 1.47x103 J from first law 3. the speed on impact. KE = 1/2(m2) where = speed KE = 1.47x103 kg m2 / s2 = 1/2(0.500 kg ) 2 = [(1.47x103 kg m2 / s2) / 0.250 kg]1/2 = 76.7 m/s 4. the temperature rise of the Cu assuming that all the thermal energy is retained by the Cu. The specific heat of Cu = 0.38 J / (g ). q = m (sp.ht.)(T) m is now mass in g q = 1.47x103 J = (500 g )( 0.38 J / g )(T) T = 7.74 2. First Law in symbols. For any change in the state of a system E = q + W a. E = Internal Energy = energy intrinsically possessed by a system (due to mass, structure, temperature, etc.) 1) E is State Function. E = change in E = Efinal - Einitial In general, the sense of is final - initial 2) If E is + , then Efinal > Einitial, the internal energy increases. If E is - , then Efinal < Einitial, the internal energy decreases. 3) Do not know the absolute values of E but are only interested in its changes. b. W is the work done on the system and q is the heat absorbed by the system. Neither W nor q are state functions, but their sum is. 3. Changes at constant volume and only PV work possible. a. At constant volume, V = 0, W = 0 b. E = qv (subscript v means constant volume) A measurement of qv gives E for the change. B. Constant Pressure Changes. (Hs)

1. Heat changes at constant pressure, only PV work possible (W = PV). a. Heat change at constant pressure qp= E W = E + PV qp = Efinal - Einitial + PVfinal- PVinitial = (E + PV)final - (E + PV)initial b. Define H = E + PV 1) H is a state function 2) Do not know the absolute values of H 3) Can measure H by measuring qp. H = qp. c. If H is + , Hfinal > Hinitial , enthalpy increases; heat is absorbed. If H is - , Hfinal < Hinitial , enthalpy decreases; heat is evolved. d. Exothermic change = one in which H is , heat is liberated. Endothermic change = one in which H is + , heat is absorbed. 2. Examples of Enthalpy Changes. a. Temperature changes at constant pressure. qp = H T 1) The proportionality constant = Cp = Molar heat capacity at constant pressure = the amount of heat energy required to raise one mole of a substance one degree Kelvin. 2) qp= H = nCpT Dimensions of Cp = J / mol K. n = number of moles. H = Enthalpy

It turns out that Cp changes slightly with temperature so H = n We use an average value of CP and will treat it as a constant. 3) Cp depends on the nature of the substance and its phase. Substance C2H5OH(l) H2O(l) H2O(g) H2O(s) Cu(s) O2(g) N2(g) Cp( J mol -1 K - 1 ) 111.46 75.30 33.58 37.64 27.15 29.36 29.12

CpdT

b. Phase Changes. 7

1) Fusion:

Solid -----> Liquid

Hfus = Molar Heat of Fusion = Heat needed to convert one mole of a solid to a liquid at a particular temperature. Dimension = J / mol 2) Vaporization: Liquid -----> Vapor Hvap = Molar Heat of Vaporization = Heat needed to convert one mole of a liquid to a gas at a particular temperature. Dimensions = J / mol 3) Sublimation: Solid ----> Vapor Hsub = Molar Heat of Sublimation = Hfus + Hvap 4) Examples Substance H2O C2H5OH C6H6 He Hfus(kJ / mol ) 6.01 4.60 9.87 0.02 Hvap(kJ / mol ) 40.7 43.4 30.8 0.08

Note that both Hfus and Hvap vary slightly with temperature. The above values are listed for the substance's Normal Freezing Point and Normal Boiling Point. The value of Hvap for H2O at 25 C = 44.0 kJ / mol. c. Heating Curve Calculate the amount of heat required to convert 20.0 g of ice at -10C to steam at 110.0C at one atm pressure. Steps: 1 2 3 H2O(s)(- 10.0C) -----> H2O(s)(0.0C) ---> H2O(l)(0.0C) ----> H4 H5 H2O(l)(100.0C) ----> H2O(g)(100.0C) ----> H2O(g)(110C) = 1 + 2 + 3 + 4 + 5 ; n = 20.0 g / 18.01 g / mol = 1.11 mol H = (1.11 mol )(37.64 J / mol K)(10.0K) + (1.11 mol)(6010 J / mol ) + (1.11 mol)(75.30 J / mol K)(100.0K) + (1.11 mol)(40,700 J / mol) + (1.11 mol)(33.58 J / mol K )(10.0 K ) = 6.10x104 J Note: of the 6.1x104 J, 5.18x104 J, or 85% of the energy, went into phase changes

d. Solution, HSoln 1) Consider the process : NaCl(s)

2 !! " Na+(aq) + Cl(aq), H = HSoln

H O

2) There are two distinct energy changes taking place. The NaCl(s) lattice must be destroyed, this requires energy = Lattice Energy HLE = 788 kJ/mol The Na+ and Cl ions are hydrated, this liberates energy, hydration energy HHydration = 784 kj/mol 3) Process NaCl(s) Na+(g) + Cl(g) HLE = 788 kJ/mol
H 2O " Na+(aq) + Cl(aq) HHydration = 784 kJ/mol Na+(g) + Cl(g) ! !

NaCl(s)

2 !! " Na+(aq) + Cl(aq), H = 788 784 = 4 kJ/mol

H O

4) If the magnitude of HLE > the magnitude of HHydration, HSoln is + If the magnitude of HLE < the magnitude of HHydration, HSoln is e. Chemical Reactions. 1) For a reaction, H = Hproducts - Hreactants 2) The absolute values of H's are not known, however, we can develop a set of Enthalpies of Formation to use in calculating H's for reactions C. Heats of Reactions. 1. Standard Enthalpies of Formation, Hf. a. Hf = H when 1 mole of a compound is prepared from its elements under standard conditions. b. Standard Conditions. 1) All gases at partial pressures of 1 atm. 2) All solutes at an effective concentration of 1 Molar. 3) All liquids and solids in their most stable form. 4) Note that no temperature is stipulated for standard conditions. Most data are reported at 25C. 5) A superscript zero ( ) indicates standard conditions. c. Examples. 1) C(s) + O2(g)( 1 atm ) ----> CO2(g)( 1 atm ) = f(CO2(g)) = 393.5 kJ / mol

2) C(s) + 1/2 O2(g)(1 atm ) ---> CO(g)( 1 atm ) = f(CO(g)) = 110.53kJ / mol In both cases C(s) = graphite--the more stable form of carbon 3) H2(g)( 1 atm ) + 1/2O2(g)( 1 atm ) ----> H2O(l) = f(H2O(l)) = 285.83 kJ / mol d. Note that f of an element = 0 e. Hfos of ions in aqueous solution are also available. These are based on f(H+(aq)) = 0 2. Uses of Hf a. Calculate 's for reactions. = f's (products) - Hf's (reactants) b. Example. Given the above Hf's, calculate H for the reaction 2CO(g) + O2(g) ----> 2CO2(g). H = 2f(CO2(g)) 2f(CO(g)) f(O2(g)) = 2( 393.51 kJ / mol) 2( 110.53 kJ / mol) 0 = 565.96 kJ / mol The kJ / mol in the final answer means per mole of the balanced equation. c. Calculate E for the reaction at 25C. Assuming ideal gas behavior, = H - (PV) = n(RT) where n = change in number of moles of gas = nproducts nreactants In this reaction, n = 2 3 = 1 E = 565.96 kJ / mol ( 1 )(8.314x103 kJ / mol K )(298k) = 563.48 kJ / mol d. Heats of combustion ( Hc) Consider the reaction CH4(g) + 2O2(g) ------> CO2(g) + 2H2O(l) This is a combustion reaction. Given the following values of Hf's, calculate the standard heat of combustion of CH4. Substance CH4(g) CO2(g) H2O(l) Hf( kJ / mol ) 74.81 393.51 285.83

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Hc = f(CO2(g)) + 2f(2O(l)) f(CH4(g)) Hc = 393.51 + 2( 285.83 ) ( 74.81 ) = 890.36 kJ / mol of CH4 Heats of combustion are easy to measure and extensive tables of c's are also available. e. Other examples. 1) Calculate H for Mg2+ + 2 OH Substance Mg2+ OH Mg(OH)2 Hf(kJ/mol) 461.96 229.94 924.66 Mg(OH)2(s)

H = Hf(Mg(OH)2(s) Hf(Mg2+) 2 Hf(OH) = 924.66 (461.96) 2(229.94) = 2.82 kJ/mol 2) Calculate H and E at 25 C for: 2 N2O(g) + 3 O2(g) Substance N2O(g) N2O(g) Hf(kJ.mol) 81.56 33.85 4 NO2(g)

H = 4 Hf(NO2) 2 Hf(N2O) 3 Hf(O2) = 4(33.85) 2 (81.56) 3-(0) = 27.72 kJ/mol E = H n RT n = 4 2 3 = 1 E = 27.72 kJ/mol (1)(8.313x103 kJ/mol K)(298 K) = 27.72 + 2.48 = 25.24

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3. Hess's Law a. Just as one can add and subtract chemical equations to give net equations, one can add and subtract their H's in the same way to give the H's for the net reactions. Example. Calculate for the reaction C2H6(g) + H2O(l) -----> CH3OH(g) + CH4(g) given the following 's. 1. 2CH3OH(g) + 3O2(g) ----> 2CO2(g) + 4H2O(l) 2. 2C2H6(g) + 7O2(g) ---> 4CO2(g) + 6H2O(l) 3. CH4(g) + O2(g) ----> CO2(g) + 2H2O(l) Note that net equation = 1/2(2) - 1/2(1) - (3) 1/2(2) = C2H6(g) + 7/2O2(g) ---> 2CO2(g) + 3H2O(l) 1/2(1) = CO2(g) + 2H2O(l) ---> CH3OH(g) + 3/2O2(g) (3) = 2H2O(l) + CO2(g) ---> CH4(g) + 2O2(g) C2H6(g) + H2O(l) -----> CH3OH(g) + CH4(g) = 1/22 = 1560 kJ = 1/21 = + 764 kJ = 3 = + 890 kJ = + 94 kJ 1 = 1528 kJ 2 = 3120 kJ 3 = 890 kJ

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Problems 1. A 50 gram object dropped from a height is observed to have a terminal velocity of 2.0 x 104 cm/s. Calculate the terminal kinetic energy of the object and the height from which the object was dropped.Neglect air resistance and assume that the acceleration of gravity is 9.8 m/s2. If the thermal energy released on impact was retained entirely by the object, calculate how much the temperature of the object would change. Assume that the specific heat of the object is 0.45 J/g-deg. 2. If a system absorbs 400 J of heat from the surroundings while it is doing 600 J of work on the surroundings, what is E for the system? 3. Give a symbolic definition of the enthalpy, H. 4. A system consists of 18 g of H2O(g) confined in a piston-cylinder with the pressure controlled at 2.0 atm at an initial temperature of 150 C. The volume of the gas at the start is 34.7 L. In a process, a change takes place and the H2O (g) is cooled from 150 C to 130 C. The volume of the H2O (g) drops to 33.1 L with the pressure still held constant at 2.0 atm, the specific heat of H2O (g) is 2.03 J/g-K. a. What is q for the system? b. What is w in joules? c. What is E? What is H? 2.0 atm 2.0 atm

H2O(g) 150 C 34.7 L 33.1 L H2O(g) 130C

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5. a. Using the heat capacity data given in the unit calculate the amount of heat that would be under constant pressure conditions, to convert 40 g of ice at -20 C to steam at 120 C.

required,

b. In an insulated system, 2.00 g of ice at 0.0 C is dropped into 50.0 g of water at 80.0 C. What will be the final temperature of the water? ************************************************************************* Use thermodynamic parameters listed in the appendix in your text in working the following problems. 6. Balance the following equations and calculate H. a) b) c) d) e) f) CH3CH2OH (l) + O2 (g) -----> CO (g) + H2O (l) C2H4 (g) + O2 (g) -----> CO2 (g) + H2O (l) NO2 (g) + H2 (g) -----> N2H4 (l) + H2O (l) N2O (g) + O2 (g) ----> NO2 (g) CO (g) + O2 (g) -----> CO2 (g) H2 (g) + O2 (g) -----> H2O (l)

7. Use Hess's Law and the values of H for the reactions in problem 6 to calculate H's for the following reactions: Be sure to balance the equations first and to use Hess's Law to obtain your answers. After you have calculated your answers using Hess's Law, the answers can be checked using Hf's. a) N2O (g) + H2 (g) -----> N2H4 (l) + H2O (l) b) C2H5OH (l) -----> C2H4 (g) + H2O (l) Answers
1. 1000J; 2.04x103m; 44 C 3. H = E + PV
5

2. 200 J

4. a. 731 J; b. 324 J; c. E = 407 J, H = 731 J

5. a. 1.24x10 J; b. 73.9 6. a) CH3CH2 OH (l) + 2 O2 (g) -----> 2 CO (g) + 3 H2 O (l) -801.4 kJ b) C2H4 (g) + 3 O2 (g) -----> 2 CO2 (g) + 2 H2O (l) -1410.9 kJ c) 2 NO2 (g) + 6 H2 (g) -----> N2 H4 (l) + 4 H2 O (l) -1160.5 kJ d) 2 N2 O (g) + 3 O2 (g) ----> 4 NO2 (g) -27.72 kJ e) 2 CO (g) + O2 (g) -----> 2 CO2 (g) -566 kJ f) 2 H2 (g) + O2 (g) -----> 2 H2 O (l) -571.6 kJ NOTE THAT THE ANSWERS MAY VARY A BIT BECAUSE VALUES OF Hf MAY VARY 7. a) N2O (g) + 3 H2 (g) -----> N2 H4 (l) + H2 O (l) b) C2 H5 OH (l) -----> C2 H4 (g) + H2 O (l) -317.0 kJ 43.5 kJ

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