CHEM 131 CHEMISTRY FOR ENGINEERS

ENTHALPY

We have established heat as the flow of energy from a body of higher temperature to a body of lower
temperature. Heat either flows from the surroundings to the reaction system(endothermic) or from the reaction
system to the surroundings(exothermic). For a reaction taking place at constant pressure, the heat flow of the
reaction system is equal to the difference in enthalpy(H) between products and reactants.

Qreaction at constant pressure = QP = H = Hproducts – Hreactants

Enthalpy is a type of chemical energy, sometimes referred to as the “heat content”. It comes from the Greek word”
enthalpos” which means “to put heat into”. This idea was made up by the Dutch scientist Heike Kamerlingh Onnes
in 1909.

• An example of a reaction that shows the enthalpy relationship between reactants and products is the
combustion of methane which is an exothermic reaction.

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) H<0

In this reaction, the products, 1 mol of CO2(g) and 2 mol of H2O(l), have lower enthalpy than the reactants, 1
mol of CH4(g) and 2 mol of O2(g). There is a decrease in enthalpy and this is the source of heat evolved to
the surroundings.

• The melting of ice is an example of an endothermic process.

H2O(s) → H2O(l) H>0

Liquid water has higher enthalpy ice, so heat must be transferred from the surroundings to melt the ice.

In general, the following reactions apply for reactions taking place at constant pressure.

Exothermic reaction: Q = H<0 Hproducts < Hreactants

Endothermic reaction Q = H>0 Hproducts > Hreactants

ENTHALPY SIGN CONVENTION

REACTION TYPE DEFINITION SIGN

EXOTHERMIC • chemical reaction evolves heat H < 0, ( negative )

• the system loses heat
• this heat loss at constant pressure
is its decrease in enthalpy

The combustion of methane is a strongly exothermic reaction:

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) H<0
The products of this reaction have lower enthalpy than the reactants.

ENDOTHERMIC • chemical reaction absorbs heat H > 0, ( positive )

from the surroundings
• the system gains heat
• this heat gained at constant
pressure is its increase in enthalpy

The formation of nitrogen dioxide in automobile engines is an an endothermic reaction

N2(g) + 2O2(g) → 2NO2(g) H>0
The products of this reaction have higher enthalpy than the reactants.

1 Prepared by: Engr. Karla Jane N. Puracan

THERMOCHEMICAL EQUATIONS

A chemical equation that shows the enthalpy relation between products and reactants is called a thermochemical
equation. This type of equation contains, at the right of the balanced chemical equation, the appropriate value
and sign for H.

Examples:

1. A simple experiment in a coffee cup calorimeter shows that when one gram of NH 4NO3 dissolves, Qrxn=351J.
The calorimeter is open to the atmosphere, the pressure is constant so that H = 351J.

When one mole of NH4NO3 dissolves, since 1 mol of NH4NO3 is equal to 80 g NH4NO3, then H should be 80
times as great.

NH4NO3(aq) → NH4+(aq) + NO3-(aq) H = 28.1 kJ

2. The formation of HCl from the elements is found to be

H2(g) + Cl2(g) → 2HCl(g) H = - 185 kJ

The thermochemical equation shows that 185 kJ of heat is evolved when 2 moles of HCl are formed from H 2
and Cl2.

CONVENTIONS FOR THERMOCHEMICAL EQUATIONS:

• The sign of H indicates whether the reaction, when carried out at constant pressure, is endothermic
(positive H) or exothermic (negative H)

• The coefficients of the thermochemical equation represent the number of moles of reactant and product

• The phases (physical states) of all species must be specified using the symbols (s), (l), (g), or (aq)

• The value of ΔH applies when products and reactants are at the same temperature, usually 25 °C

RULES IN THERMOCHEMISTRY:

• The magnitude of H is directly proportional to the amount of reactant or product.

• ΔH for the reaction is equal in magnitude but opposite in sign for ΔH for the reverse of the reaction.

Examples:

1. Red phosphorus reacts with liquid bromine in an exothermic reaction

2P(s) + 3Br2(l) → 2PBr3(g) H = −243kJ

Calculate the enthalpy change when 2.63 g of phosphorus reacts with an excess of bromine in this way.

Solution:

1mol
number of moles of P = 2.63gx = 0.0849 mol P
30.97g

−243kJ
H = 0.0849molx = −10.3 kJ
2mol

At constant pressure, there will be 10.3 kJ of heat released for every 2.63 g of phosphorus.

2 Prepared by: Engr. Karla Jane N. Puracan

 2. Hydrazine reacts with chlorine according to the equation

N2H4(l) + 2Cl2(g) → 4HCl(g) + N2(g) H = −420kJ

Calculate the enthalpy change when

(a) 25.4 g of hydrazine reacts with excess chlorine

(b) when 1.45 mol of HCl(g) is generated by this reaction

Solution:

(a) molar mass N2H4 = 2N + 4H = 2(14 g/mol) +4(1g/mol) = 32 g/mol

1mol
number of moles N2H4 = 25.4gx = 0.79375 mol
32g

−420kJ
H = 0.79375molx = −333.38 kJ
1mol

At constant pressure, there will be 333.38 kJ of heat released for every 25.4 g of hydrazine.
−420kJ
(b) H = 1.45molx = −152.25 kJ
4mol

At constant pressure, there will be 152.25 kJ of heat released for every 1.45 moles of hydrogen
chloride released.

3. Calculate the enthalpy change when 1.00 g of the underlined substance is consumed or produced.

(a) Ca(s) + Br2(l) → CaBr2(s) H= -683 kJ

Solution:

molar mass Br2 = 2Br = 2(79.9 g/mol) = 159.8 g/mol

1mol
number of moles Br2 = 1.00gx = 6.26x10-3 mol
159.8g

−683kJ
H = 6.26x10−3 molx = −4.27 kJ
1mol

At constant pressure, there will be 4.27 kJ of heat released for every 1 g of Br 2.

(b) 6Fe2O3(s) → 4Fe3O4(s) + O2(g) H= 472 kJ

Solution:

molar mass Fe3O4 = 3Fe + 4O = 3(55.85 g/mol) + 4(16 g/mol) = 231.55 g/mol

1mol
number of moles Fe3O4 = 1.00gx = 4.32x10-3 mol
231.55g

472kJ
H = 4.32x10−3 molx = 0.51 kJ
4mol

At constant pressure, there will be 0.51 kJ of heat absorbed for every 1 g of Fe 3O4.

(c) 2NaHSO4(s) → 2NaOH(s) + 2SO2(g) + O2(g) H= 806 kJ

Solution:

molar mass NaHSO4 = Na + H + S +4O

= 23 g/mol + 1 g/mol + 32 g/mol + 4(16g/mol) = 120 g/mol

1mol
number of moles NaHSO4 = 1.00gx = 8.33x10-3 mol
120g

806kJ
H = 8.33x10−3 molx = 3.36 kJ
2mol

At constant pressure, there will be 3.36 kJ of heat absorbed for every 1 g of NaHSO4.

3 Prepared by: Engr. Karla Jane N. Puracan

 More Problems:

1. Calculate the amount of heat required to decompose 4 moles of ferric oxide as shown in the equation

Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g) + 26.3kJ

Solution:

Based on the balanced chemical equation, 26.3 kJ of heat is released for every 1 mol of Fe2O3(s) reacted with excess CO(g).

H = 4molFe2O3x −26.3kJ = -105.2 kJ

1molFe2O3

At constant pressure, there will be 105.2 kJ of heat released for every 4 moles Fe2O3.

2. Calculate the amount of heat absorbed when 35 g of carbon disulfide is formed.

3C(s) + 6S(s) → 3CS2(g) H = 89.3kJ

Solution:

molar mass CS2 = C + 2S = 12g/mol + 2(32 g/mol) = 76 g/mol

1mol
number of moles CS2 = 35gx = 0.46 mol
76g

89.3kJ
H = 0.46molx = 13.71 kJ
3mol

At constant pressure, there will be 13.71 kJ of heat absorbed for every 3 moles CS2.

3. A chemist mixes 1.00 g of CuCl2 with an excess of (NH4)2HPO4 in dilute aqueous solution. He measures
the evolution of 670 J of heat as the two substances react to give Cu 3(PO4)2(s). Compute the enthalpy
change that would result from the reaction of 1.00 mol CuCl 2 with an excess of Cu3(PO4)2(s).

CuCl2 + (NH4)2HPO4(aq) → Cu3(PO4)2(s)

Solution:

molar mass CuCl2 = Cu + 2Cl = 63.55g/mol + 2(35.45 g/mol) = 134.45 g/mol

since H for every 1 g CuCl2 = −670 J

134.45g −670J
H for every 1mol CuCl2 = 1molx x = −90,081.50 J
1mol 1g

At constant pressure, there will be 90,081.50 J of heat released for every 1 g of CuCl2.

MORE PROBLEMS

In the late 18th century, Priestly prepared ammonia by reacting HNO3(g) with H2(g) as shown in the
equation:

HNO3(g) + 4H2(g) → NH3(g) + 3H2O(g) + 637 kJ

(a) Calculate H when 1 mole of hydrogen gas reacts.

Solution:

−637kJ
H for every 1mol H2 = 1molx = −159.25 kJ
4mol

At constant pressure, there will be 159.20 J of heat released for every 1 mol of H2(g).

(b) What is H when 10 g of NH3(g) is produced?

Solution:

molar mass NH3 = N + 3H = 14g/mol + 3(1 g/mol) = 17 g/mol

1mol
number of moles NH3 = 10gx = 0.59 mol
17g

−637kJ
H = 0.59molx = -374.71 kJ
1mol

4 Prepared by: Engr. Karla Jane N. Puracan

 At constant pressure, there will be 374.71 kJ of heat released for every 10 g NH3.

(c) Find the mass of HNO3(g) reacted when 800 kJ of heat is released.

Solution:

molar mass HNO3 = H + N + 3O = 1 g/mol + 14g/mol + 3(16 g/mol) = 63 g/mol

1mol
moles of HNO3 reacted to release 800 kJ of heat = 800kJx = 1.26 mol
−637kJ

63g
moles of HNO3 reacted to release 800 kJ of heat = 1.26molx = 79.12 g
1mol

At constant pressure, 79.12 g HNO3 needed to release 800 kJ of heat.

PHASES CHANGES

We recall that there are four phases or states of matter: solid, liquid, gas, and plasma. When a substance changes
from one state of matter to another, we say that it has undergone a change of state or a change of phase.

These changes of phase always occur with a change of heat. Heat, which is energy, either comes into the material
during a change of phase or heat comes out of the material during this change. This heat needed to change the
phase of a substance from one form to another is called latent heat of transformation. Because these phase
changes generally take place at constant pressure, the corresponding heat flows are viewed as changes in
enthalpy.

It is important to note that although the heat content of the material changes when a phase change occurs, the
temperature does not. During a change in phase, the heat energy is used only to change the bonding between
molecules.

Melting Point and Boiling Point

If a solid is heated through its melting point, it will melt and

turn to liquid. Some substances—for example, dry ice (solid carbon
dioxide)—cannot exist as a liquid at certain pressures and
will sublimate instead, turning directly into gas. If a liquid is cooled
through its melting point, it will freeze.
If a liquid is heated through its boiling point, it will vaporize
and turn to gas. If a gas is cooled through its boiling point, it will
condense into a liquid, or sometimes deposit into a solid, as in the case
of carbon dioxide.

A substance requires a certain amount of heat to undergo a phase change. If you were to apply steady heat to a
block of ice, its temperature would rise steadily until it reached 0ºC. Then the temperature would remain constant
as the block of ice slowly melted into water. Only when all the ice had become water would the temperature
continue to rise.

5 Prepared by: Engr. Karla Jane N. Puracan

 Description of Term for Phase Heat Movement During Temperature Change
Type of Reaction
Phase Change Change Phase Change During Phase Change

Heat goes into the solid as it

Solid to Liquid Melting Endothermic
melts

Heat leaves the solid as it

Liquid to Solid Freezing Exothermic
freezes

Vaporization,

which Heat goes into the liquid as it

Liquid to Gas includes Endothermic none
vaporizes
boiling and
evaporation

Heat leaves the gas as it

Gas to Liquid Condensation Exothermic
condenses

Heat goes into the solid as it

Solid to Gas Sublimation Endothermic
sublimates

The amount of heat that is absorbed when melting occurs at constant pressure is called latent heat of
fusion or enthalpy of fusion, Hf..

The amount of heat required for the vaporization of a quantity of liquid at constant temperature and
pressure is called latent heat of vaporization or enthalpy of vaporization, Hv.

The enthalpy change that accompanies the melting of one mole of a substance is called its molar enthalpy
of fusion.

The enthalpy change that accompanies the vaporization of one mole of a substance is called its molar
enthalpy of vaporization.

When a liquid is converted into gas, all the molecules in the sample must overcome whatever
intermolecular forces are present. This means that energy must flow into the substance to vaporize it, so
the heat of vaporization will always be positive. It follows that the reverse process, condensation, will
always release heat.

The values of enthalpy changes in opposite directions have the same numeric value and differ only in their
signs. Because the strength of the intermolecular forces varies from one substance to another, the
magnitude of the enthalpy change for any phase transition will also depend on the substance involved.

The data in table A allow us to calculate the heat required for phase transition involving any particular
sample of a substance:

H = nHphase change

= nHphase change

where: H = heat absorbed or released

n = number of moles of a substance

m = mass of substance

Hphase change = enthalpy of fusion or vaporization

6 Prepared by: Engr. Karla Jane N. Puracan

 TABLE A. MOLAR ENTHALPIES OF FUSION AND VAPORIZATION

Substance Hfus Hfus Hvap Hvap

(kJ/mol) (J/g) (kJ/mol) (J/g)

NH3 5.65 332.35 23.35 1373.53

HCl 1.992 54.65 16.15 443.07

CO 0.836 29.86 6.04 215.71

CCl4 2.5 16.25 30.0 195.06

H20 6.007 333.72 40.66 2258.89

NaCl 28.8 492.73 170 2908.47

C6H6 9.84 126.15 30.8 394.87

Br2 10.8 67.58 29.6 185.22

Hg 2.33 11.62 59.4 296.13

C10H8 19.3 150.78 43.3 338.28

Examples:

1. Find the enthalpy change required to change 2.6 kg of ice at 0C into water at the same temperature?

Solution:

molar mass H20 = 2H + O = 2(1g/mol) +16g/mol = 18 g/mol

1000g 1mol
number of moles H20 = 2.6kgx x = 144.44 mol
1kg 18g

H = nHfus

6.007kJ
= 144.44molx
1mol

= 867.68 kJ

The enthalpy change required to melt 2.6 kg of ice at 0C into water at the same temperature is
867.68 kJ.

2. Find the enthalpy change required to transform 3.7 kg of steam at 100C into water at the same
temperature?

Solution:

molar mass H20 = 2H + O = 2(1g/mol) +16g/mol = 18 g/mol

1000g 1mol
number of moles H20 = 3.7kgx x = 205.56 mol
1kg 18g

H = nHcond

−40.66kJ
= 205.56molx
1mol

= −8357.89 kJ

7 Prepared by: Engr. Karla Jane N. Puracan

 The enthalpy change required to transform 3.7 kg of steam at 100C into water at the same
temperature is 8357.89 kJ.

3. Calculate the enthalpy change when 2.38 g of carbon monoxide (CO) vaporizes at its normal boiling
point.

Solution:

molar mass CO = C + O = 12g/mol +16g/mol = 28 g/mol

1mol
number of moles CO = 2.38gx = 0.085 mol
28g

H = nHvap

6.04kJ
H = 0.085molx = 0.51 kJ
1mol

The enthalpy change of the vaporization of CO at its normal boiling point is 0.51 kJ.

4. The vaporization of 100.0 g of carbon tetrachloride requires 19.95 kJ of heat at its normal boiling
point, 349.9K, and a pressure of 1 atm. Calculate the molar enthalpy of vaporization of CCl 4 under
these conditions.

Solution:

molar mass CCl4 = C + 4Cl = 12g/mol + 2(35.45 g/mol) = 153.8 g/mol

1mol
number of moles CCl4 = 100gx = 0.6502 mol
153.8g

19.95kJ
Hv = 1molx = 30.68 kJ
0.6502mol

The molar enthalpy of vaporization of CCl4 at the given conditions is 30.68 kJ.

5. The melting of 0.140 g of Br2(which occurs at –7.2C) absorbs 9.43 J of heat at constant pressure.
Compute the enthalpy change of 2.00 mol of Br2 when it freezes.

Solution:

molar mass Br2 = 2Br = 2(79.90 g/mol) = 159.8 g/mol

1mol
number of moles 0.140 g Br2 = 0.140gx = 8.76 x 10-4 mol
159.8g

enthalpy change to melt 1 mol of Br2

9.43J
Hfus = 1molx = 10763.67 J
8.76x10−4 mol

enthalpy change to freeze 2 mol of Br2

−10763.67J
Hfreezing = 2molx = –21,527.34 J
1mol

The enthalpy change of 2.00 mol of Br2 when it freezes is 21,527.34 J.

6. Molten sodium chloride is used for making elemental sodium and chlorine. Suppose the electrical
power to a vat containing 56.2 kg of molten sodium chloride is cut off, and the salt crystallizes
without changing its temperature. Calculate the enthalpy change.

Solution:

molar mass NaCl = Na + Cl = 23 g/mol + 35.45g/mol= 58.45 g/mol

1mol
number of moles NaCl = 56.2gx = 0.96 mol
58.45g

H = −nHf

28.8kJ
H = − 0.96molx = −27.69 kJ
1mol

The enthalpy needed to solidify the molten sodium chloride is 27.69 kJ.

8 Prepared by: Engr. Karla Jane N. Puracan

 7. Calculate the enthalpy change when 50 g of ice at −30C is heated to completely melt to liquid water
at 0.0C.

Solution:

molar mass H20 = 2H + O = 2(1g/mol) +16g/mol = 18 g/mol

H1(from −30C to −0C) → H2(ice to water at 0C)

HT = H1 + H2

= (mcpT)ice + nHfus

1mol 6007J
= 50g(2.09 J/gC)(0+30)C + 50gx x
18g 1mol

= 3135 J + 16,686,11 J

HT = 19,821.11 J

The enthalpy needed to change 50 g of ice at −30C into water at 0C is 19,821.11 J.

8. Find the enthalpy needed to change 1900 g of ice at −10C into water at 10C.

Solution: H1(from −10C to −0C) → H2(ice to water at 0C) → H3(from 0C to 10C)

molar mass H20 = 2H + O = 2(1g/mol) +16g/mol = 18 g/mol

HT = H1 + H2 + H3

= (mcpT)ice + nHfus + (mcpT)water

1mol 6007kJ
= 1900g(2.09 J/gC)(0+10)C + 1900gx x + 1900g(4.184 J/gC)(10 – 0)C
18g 1mol

= 39,710 J + 634072.22 J + 79,496 J

= 753,278.22 J

The enthalpy needed to change 1900 g of ice at −10C into water at 10C is 753, 278.22 J.

9. You have a supply of ice at 0.0C and a glass containing 150 g of water at 25C. How many grams of
ice must be added to the glass (and melted) to reduce the temperature of water to 0C?

Solution: H1(ice to water at 0.0C)

H2(water from 25C to 0C)

H1 = −H2

mHf = − mcpT(water)

 333.72J 
m  = − 150g(4.184J/gC)(0C – 25C)
 g 

333.72m = – 15,690

m = 47.02 g

47.02 g of ice must be added to the 150g water to reduce its temperature to 0C.

10. An ice cube weighing 36.9 g and having a temperature of 0.0C is dropped into 360 g of water that
has a temperature of 20.0C. Calculate the final temperature that will be reached by the mixture,
assuming no heat loss to the surroundings.

Solution:

H1(ice to water at 0.0C)

H2(melted ice to final temperature)

H3(water from 20C to final temperature)

H1 + H2 = − H3

9 Prepared by: Engr. Karla Jane N. Puracan

 333.72J
36.9gx + 36.9g(4.184 J/gC)(T – 0C) = − 360g(4.184J/gC)(T – 20C)
g

12,314.268 + 154.3896(T – 0C) = − 1506.24(T – 20C)

12,314.268 + 154.3896T = − 1506.24T + 31,124.8

1660.6296T = 18,810.532

1660.6296T = 17,810.45

T = 10.73C

The final temperature reached by the mixture is 10.73C.

11. Lead melts at 327C. An enthalpy change of 28,052 J is added to a 1.5 kg piece of lead that is at
300C. How much of the lead melts if its specific heat is 130 J/kgC and its enthalpy of fusion is 24,700
J/kg?

Solution:

H1(from 300C to 327C)

H2(solid to liquid lead at 327C)

Enthalpy change needed to melt 1.5 kg Pb at 300C to Pb at 327C

HT = H1 + H2

= (mcpT)Pb + nHfus

24700J
28,052 = 1.5kg(130 J/kgC)(327 – 300)C + m•
1kg

= 5265 + 24,700m

22,787 = 24700m

m = 0.92 kg

Only 0.92kg of Pb is melted with a 28,052 J enthalpy change.

PRACTICE PROBLEMS:

1. Calculate the enthalpy change when 14.5 g of sodium chloride melts.

2. The heat of fusion of pure silicon is 43.4 kJ/mol. Find the enthalpy change needed to melt a 5.24 g sample of
silicon at its melting point of 1693K.

3. The enthalpy of vaporization of acetone is 31.3 kJ/mol. If 1.40 kg of water were vaporized to steam in a boiler,
how much acetone (in kg) would need to be vaporized to use the same enthalpy change?

4. Calculate the enthalpy change needed to convert 1.70 g of ice originally at –12.0C into steam at 105C.

5. A sample of ice at −25C is placed into 80g of water initially at 90C. If the final temperature of the mixture is
20C, what was the mass of the ice?

6. A 50-g sample of ice at −8C is placed into 300g of water at 70C. Find the final temperature of the mixture
assuming that the ice sample completely melts.

7. A 45-g sample of steam at 116C are bubbled into 300 g water at 10C. Find the final temperature of the
system, assuming that the steam condenses into liquid water.

10 Prepared by: Engr. Karla Jane N. Puracan