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Enthalpy Exercises

The document provides sample questions and problems related to thermodynamics. It includes terms and concepts, enthalpy change diagrams, calculations of properties like ∆H, ∆U, q, and w for various processes, and sample problems to calculate values like work, enthalpy of reaction, heat capacity, and temperature change. It examines concepts like isolated vs non-isolated systems, exothermic and endothermic processes, reversible processes, and heats of reaction, vaporization and combustion.

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25 views

Enthalpy Exercises

The document provides sample questions and problems related to thermodynamics. It includes terms and concepts, enthalpy change diagrams, calculations of properties like ∆H, ∆U, q, and w for various processes, and sample problems to calculate values like work, enthalpy of reaction, heat capacity, and temperature change. It examines concepts like isolated vs non-isolated systems, exothermic and endothermic processes, reversible processes, and heats of reaction, vaporization and combustion.

Uploaded by

mpumelaqq
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Sample quiz and test questions – Chapter 2.

I. Terms and short answers

1. A system that can exchange neither matter nor energy with its surroundings is called

isolated

2. A process that releases heat into the surroundings is called

exothermic

3. Work needed to raise a mass m through a height h on the surface of the Earth is given by
equation

w = mgh

4. Work of isothermal compression of an ideal gas can be calculated using the equation

w = -nRTln(Vf/Vi)

5. A reversible process is defined as

A process that can be reversed by an infinitesimal change in a parameter

6. The internal energy is

The sum of all kinetic, potential, rotational, vibrational, and electronic energy of all
the atoms, ions, and molecules in the system

II. Sketch the enthalpy change diagram for the following processes and reactions:

1. CO2(g) à CO2(s) ∆depHo = - 33.56 kJ

2. C(gr) + 2S(s) à CS2(l) ∆fHo = 88 kJ


∆H
CO2(g) ∆H
CS2(l)

∆depH
∆fH

CO2(s)

C(gr) + 2S(s)

III. Calculations of ∆H, ∆U, q, and w.

Calculate the quantities ∆H, ∆U, q, and w for the following processes. Be sure to give signs!
Gases may be considered ideal, and the volumes of liquids and solids (but not gases) may be
ignored. Thermodynamic data are in Appendix A1.2.

initial state final state


(1) 0.3 N2 (g), 300 K, 1 bar → 0.3 N2 (g), 300 K, 0.1 bar

if this expansion occurs against a constant external pressure of 0.05 bar.

w = -pext*∆V Vi = 0.0075 m3 Vf = 0.075 m3

w = - (.05*10^5) * 0.067 = - 340 J q = ∆U - w = +340 J

∆U=0 (isothermal, ideal gas; U for an ideal gas depends only on T)

∆H = ∆U + ∆(pV); pV = nRT (ideal gas);

∆(pV) = nR(∆T) = 0 (isothermal, ideal gas) ∆H = ∆U = 0

initial state final state


(2) 0.3 N2 (g), 300 K, 1 bar → 0.3 N2 (g), 300 K, 0.1 bar

if this expansion occurs reversibly, with pext = pgas.

w = - nRT ln(Vf/Vi) (see p. 45)


w = - 1720 J q = ∆U - w = +1720 J; ∆U = 0 (isothermal, ideal gas)

∆H = ∆U + ∆(pV) = 0 (isothermal, ideal gas)

initial state final state


(3) 0.3 N2 (g), 300 K, 1 bar → 0.3 N2 (g), 300 K, 0.0 bar

expansion into a vacuum, pext = 0.


w=0, q = 0, ∆U=0, ∆H=0

initial state final state


(4) 1 g Au(s), 273 K, 1 bar → 1 g Au(s), 373 K, 1 bar

with pext = 1 bar.

w = -pext∆V = 0; (no gases involved, volume changes are negligible)

∆H = qp = n*Cp,m*(∆T) = (1/197)*25.42*100 = 12.9 J

Cp,m = 25.42 J-mol-1-K-1 (Appendix A1.2)

∆U = ∆H - ∆(pV) = ∆H = 12.9 J (ignore volume changes)

initial state final state


(5) CaO(s) + CO2(g) → CaCO3(s)

with all reactants and products at 298 K, 1 bar.

∆H° = ∆fH°(CaCO3(s)) - ∆fH°(CaO(s)) - ∆fH°(CO2(g))

∆H° = (-1206.9) - (-635.1) - (-393.5) = -178.3 kJ ∆H°=qp = -178.3 kJ

w = -pext∆V = - (1.00*105 Pa) * (-n*R*T/pgas) = +2480 J (neg ∆V gives pos w)

∆U = q + w = -178.3 + 2.5 = -175.8 kJ

initial state final state


(6) 10 g H2O, solid, 250 K, 1 bar → 10 g H2O, liquid, 350 K, 1 bar
∆H1 ∆H2 ∆H3
3 steps: (solid at 250K → solid at 273 K→ liquid at 273 K → liquid at 350K)

∆H1 = n * Cp,m(H20(s)) * ∆T = (10/18) * 37 * (273-250) = +473 J (Table 2.1)


∆H2 = n * Cp,m(H20(s)) * ∆T = (10/18) * 6010 = +3340 J (Table 2.2)
∆H3 = n * Cp,m(H20(l)) * ∆T = (10/18) * 75.3 * (350-273) = +3220 J (Table 2.1)

∆H = q = +7030 kJ ∆U = ∆H (no gases involved) w = 0 (no gases involved)

IV. Problems

1. 0.850 mol of an ideal gas initially at a pressure of 15 atm and 300 K is allowed to expand
isothermally until its final pressure is 2 atm. Calculate the wotk done if the expansion is
carried out against a constant external pressure of 1 atm.

n = 0.85 p1 = 15 atm T = const = 300 K


p2 = 2 atm pext = 1 atm = 101325 Pa
p1V1 = nRT à V1 = nRT/p1 = 0.85x0.082x300/15 L = 1.39 L
at const temp. p1V1 = p2V2 à V2 = p1V1/p2 = 15x1.39/2 L = 10 46 L
w = -pext∆V = -101325 Pa (10.46 - 1.39)x10-3m3 = -919 J

2. What is the specific heat capacity of a compound that rose in temperature by 2.54oC when
its sample of a mass 5 g was supplied with 346 J of heat.

C = q/(m∆T) = 346J/(5g x 2.54K) = 27.24 J/(g K)

3. When 0.9862 g of benzoic acid was burned in a bomb calorimeter, the temperature rose
from 21.84oC to 25.67oC. What is the heat capacity of the calorimeter?
In a separate experiment a quantity of 0.4654 g of glucose was burned in the same calorimeter
and the temperature rose from 21.22 oC to 22.28oC. Calculate the enthalpy of combustion of
glucose.

Information from the tables:


Benzoic acid: C6H5COOH, Mw = 122.13 g/mol, ∆combHo = -3227 kJ/mol
Glucose: C6H12O6, Mw = 180.16 g/mol
n(benzoic acid) = 0.9862g/122.13 g/mol = 0.0081 mol
heat supplied to the calorimeter q = 0.0081mol x 3227kJ/mol = 26.06 kJ
C = q/∆T = 26.06J/(25.67 - 21.84)K = 6.8 kJ/K
n(glucose) = 0.4654g/180.16g/mol = 0.0026mol
heat evolved by cobustion of glucose sample q = C∆T = 6.8 kJ/K x (22.28 - 21.22)K =
7.21 kJ
∆combHo(glucose) = -q/n = -7.21kJ/0.0026mol = -2772 kJ/mol
4. From the following data, calculate the enthalpies of transformations from the more stable
form to the less stable form:

1. C(graphite) + O2(g) à CO2(g) ∆rxnHo1 = -393.51 kJ

2. C(diamond) + O2(g) à CO2(g) ∆rxnHo2 = -395.41 kJ

3 = 2 - 1 : C(d) à C(gr)
∆rxnH3 = ∆rxnH2 - ∆rxnH1 = -395.41kJ -(-393.51)kJ = -1.9 kJ

5. The enthalpies of hydrogenation of ethylene and benzene have been determined at 298 K:

C2H4(g) + H2(g) à C2H6(g) ∆rxnHo = -132 kJ

C6H6(g) + 3H2(g) à C6H12(g) ∆rxnHo = -246 kJ

What would be the enthalpy of hydrogenation of benzene if it contained three isolated,


unconjugated double bonds? How would you account for the difference between the calculated
value based on this assumption and the measured value?

The enthalpy of hydrogenation would be -396 kJ. The difference between the measured
and calculated value can be explained as follows: in hydrogenation of a double bond the
resultant heat is the difference between the energy required to break C=C bond and form
two C-H bonds. This difference will be greater negative value for 3 separate double bonds
than for benzene due to the delocalization energy.

6. Metabolic activity in the human body releases about 1x104 kJ of heat per day. Assuming
that the body is 50 kg of water, what temperature rise would the body experience if it were an
isolated system? How much water must the body eliminate as perspiration to maintain the
normal body temperature (98.6oF). The heat of vaporization of water may be taken as 2.41 kJ/g
and the specific heat capacity as 4.18 J/gK.

∆H = 1x104kJ = 1x107J = mC∆T à ∆T = 1x107J/(5x104g x 4.18J/gK) =47.85K


∆H = m x ∆vapH à m = 1x104kJ/2.41 kJ/g = 4149g = 4.14 kg

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