Thermochemistry Part I

ELFRIDA GINTING, PH.D

ELFRIDA GINTING, PH.D 1

Forms of Energy

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Interconversion of Energy

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Heats of Reactions and Calorimetry

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 Constant-Pressure Calorimetry
❖∆𝐻 is defined as the heat flow at constant pressure

❖Measurements made using a constant-pressure calorimeter

❖A device used to measure enthalpy changes in chemical processes at

constant pressure

❖This device is particularly well suited to studying reactions carried out in

solution at a constant atmospheric pressure.

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A Coffee Cup Calorimeter

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 Simpler Example
❖High-temperature substance: a hot piece of metal (M)
❖Low-temperature substance: cool water (W)
❖If we place the metal in the water, heat will flow from M to W
❖The temperature of M will decrease, and the temperature of W will increase
❖Until the two substances have the same temperature
𝑞𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑀 + 𝑞𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑊 = 0
The relationship can be summarized to show that the heat gained by substance M
is equal to the heat lost by substance W
𝑞𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑀 = −𝑞𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑊

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In A Simple Calorimeter Process

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Example
A 360 g piece of rebar (a steel rod used for reinforcing concrete) is
dropped into 425 mL of water at 24°C. The final temperature of the
water was measured as 42,7°C. Calculate the initial temperature of
the piece of rebar. Assume the specific heat of steel is approximately
𝐽
the same as that for iron (0,449 ) and that all heat transfer occurs
𝑔°𝐶
between rebar and the water (there is no heat exchange with the
surroundings).

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 Answer
❖The temperature of the water increase from 24°𝐶 to 42,7°𝐶, so the water
absorbs the heat
❖Assuming all the heat transfer occur between the rebar and water, with no heat
‘lost’ to the surroundings, then
𝑞𝑟𝑒𝑏𝑎𝑟 = −𝑞𝑤𝑎𝑡𝑒𝑟
(𝑐 × 𝑚 × ∆𝑇)𝑟𝑒𝑏𝑎𝑟 = −(𝑐 × 𝑚 × ∆𝑇)𝑤𝑎𝑡𝑒𝑟
Letting f = final and i = initial
𝑐𝑟𝑒𝑏𝑎𝑟 × 𝑚𝑟𝑒𝑏𝑎𝑟 × 𝑇𝑓 − 𝑇𝑖 = − 𝑐𝑤𝑎𝑡𝑒𝑟 × 𝑚𝑤𝑎𝑡𝑒𝑟 × 𝑇𝑓 − 𝑇𝑖
𝑟𝑒𝑏𝑎𝑟 𝑤𝑎𝑡𝑒𝑟

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 Answer
𝑔
❖The density of water is 1,0 , so 425 mL of water is equal to 425 g
𝑚𝐿
❖The final temperature of both rebar and water is 42,7°𝐶 then

𝐽 𝐽
0,449 × 380 𝑔 × 42,7 − 𝑇𝑖 𝑟𝑒𝑏𝑎𝑟 = 4,184 × 425 𝑔 × 42,7°𝐶 − 24°𝐶
𝑔°𝐶 𝑔°𝐶
6902,03 𝐽 − 161,64 𝑇𝑖 = −33252,34 𝐽
𝑇𝑖 𝑟𝑒𝑏𝑎𝑟 = 248°𝐶

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 Heat Involves in Chemical Reactions
❖Because energy is neither created nor destroyed during chemical reactions,
there is no overall energy change during the reaction
❖The heat produced or consumed in the reaction (the “system”), 𝑞𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 plus
the heat absorbed or lost by the solution (the “surroundings), 𝑞𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 must
add up to zero
𝑞𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 + 𝑞𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 0
❖This means the amount of heat produced or consumed in the reaction equals
the amount of heat absorbed or lost by the solution:
𝑞𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = −𝑞𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

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 ∆𝐻
❖Because the heat released or absorbed at constant pressure is
equal to ∆𝐻, the relationship between heat and ∆𝐻𝑟×𝑛 is

∆𝐻𝑟×𝑛 = 𝑞𝑟×𝑛 = −𝑞𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 = −𝑚𝐶𝑠 ∆𝑇

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Example
When 5,03 g of potassium hydroxide are dissolved in 100,0 mL of
distilled water in a coffee-cup calorimeter, the temperature of the
liquid increases from 23°𝐶 to 34,7°𝐶. The density of water in this
𝑔
temperature range averages 0,9969 3 . What is ∆𝐻𝑠𝑜𝑙𝑛 (in kilojoule
𝑐𝑚
per mole)? Assume that the calorimeter absorbs a negligible amount
of heat and because of the large volume of water, the specific heat
of the solution is the same as the specific heat of pure water.
Given: mass of substance, volume of solvent, and initial and final
temperatures
Asked for: ∆𝐻𝑠𝑜𝑙𝑛

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 Answer
❖Calculate the mass of the solution from its volume and density.
𝑔
100 𝑚𝐿 𝐻2 𝑂 × 0,9969 + 5,03 𝑔 𝐾𝑂𝐻 = 104,72 𝑔
𝑚𝐿
❖Calculate the temperature change of the solution: 34,7°𝐶 − 23,0°𝐶 = 11,7°𝐶
❖Because the solution is not very concentrated (approximately 0,9 M), we
assume that the specific heat of the solution is the same as that of water. The
heat flow that accompanies dissolution is thus
𝐽
𝑞𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 = 𝑚𝐶𝑠 ∆𝑇 = 104,72 𝑔 × 4,184 × 11,7°𝐶 = 5130 𝐽
𝑔°𝐶
= 5,131 𝑘𝐽
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Constant-Volume Calorimetry
❖Constant-pressure calorimetry are not very well suited for studying
reactions in which one or more of the reactions is a gas

❖Such as a combustion reaction

❖The enthalpy changes that accompany combustion are therefore

measured using a constant-volume calorimeter, such as the bomb
calorimeter

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A Bomb Calorimeter
❖The heat released by a reaction
carried out at constant volume is
identical to the change in
internal energy (∆𝑼) rather
than the enthalpy change (∆𝐻)

❖∆𝑈 < ∆𝐻

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 ∆𝑇 𝑎𝑛𝑑 ∆𝐻𝑐𝑜𝑚𝑏
∆𝐻𝑐𝑜𝑚𝑏 < 𝑞𝑐𝑜𝑚𝑏 = 𝑞𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 = 𝐶𝑐𝑜𝑚𝑏 × ∆𝑇
❖Where 𝐶𝑐𝑜𝑚𝑏 is the total heat capacity of the steel bomb and the
water surrounding it.
❖To measure the heat capacity of the calorimeter:
❖Burn a carefully weighed mass of a standard compound whose
enthalpy of combustion is accurately known.
❖Example Benzoic acid (release 26,38 kJ heat per gram or ∆𝐻𝑐𝑜𝑚𝑏 =
− 26,38 𝑘𝐽/𝑔)

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Example
The combustion of 0,579 g benzoic acid in a bomb calorimeter
caused a 2,08°𝐶 increase in the temperature of the calorimeter. The
chamber was the emptied and recharged with 1,732 g of glucose and
excess oxygen. Ignition of glucose resulted in a temperature increase
of 3,64°𝐶. What is the ∆𝐻𝑐𝑜𝑚𝑏 of glucose?
Given : mass and ∆𝑇 for combustion of standard and sample
Asked for : ∆𝐻𝑐𝑜𝑚𝑏 of glucose

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Answer
❖Calculate 𝑞𝑐𝑜𝑚𝑏 from ∆𝑇 and mass of benzoic acid

𝑘𝐽
𝑞𝑐𝑜𝑚𝑏 = 0,579 𝑔 × −26,38 = −15,3 𝑘𝐽
𝑔

𝑞𝑐𝑜𝑚𝑏
−𝐶𝑐𝑜𝑚𝑏 =
∆𝑇

−15,3 𝑘𝐽 𝑘𝐽
−𝐶𝑐𝑜𝑚𝑏 = = 7,34
2,08°𝐶 °𝐶
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Answer
❖Use the heat capacity of the bomb to calculate the amount of heat
release during the combustion of glucose
𝑞𝑏𝑜𝑚𝑏 = −𝐶𝑏𝑜𝑚𝑏 × ∆𝑇
𝑘𝐽
𝑞𝑏𝑜𝑚𝑏 = −7,34 × 3,64°𝐶 = −26,7 𝑘𝐽
°𝐶
❖Because the combustion of 1,732 g of glucose released 26,7 kJ of energy,
the ∆𝐻𝑐𝑜𝑚𝑏 of glucose is
−26,7 𝑘𝐽 𝑔 𝑘𝐽
∆𝐻𝑐𝑜𝑚𝑏 = × 180.16 = −2780
1,732 𝑔 𝑚𝑜𝑙 𝑚𝑜𝑙
3
𝑘𝐽
∆𝐻𝑐𝑜𝑚𝑏 = 2,78 × 10
𝑚𝑜𝑙

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Work
❖Energy is the capacity to do work
❖Only consider mechanical work and focus on the work done during
changes in the pressure or the volume of gas
❖Mechanical Work: energy required to move an object a distance d
when opposed by a force F, such as gravity:
w= 𝐹 × 𝑑
❖With w is work
❖F is opposing force
❖d is distance

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Work
❖Because the force (F) that opposes the action is equal to the mass
(m) of the object times its acceleration then

𝑤 =𝑚×𝑎×𝑑
❖With w is work
❖m is mass
❖a is acceleration
❖d is distance

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Work is not a state of function

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Work and Chemical Reactions
❖The change in energy ∆𝑈 is equal to the sum of the heat
produced and the work performed
❖Work done by gas is called pressure-volume work (PV work)
❖A reaction that produces gas
𝐶𝑢 (𝑠) + 4𝐻𝑁𝑂3 (𝑎𝑞) → 𝐶𝑢 𝑁𝑂3 2 (𝑎𝑞) + 2𝑁𝑂2 (𝑔)
❖If the reaction is carried out in a closed system that is maintained
at constant pressure by a moveable piston, the piston will rise as the
nitrogen dioxide is formed

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Work and Chemical Reactions
❖At a constant external pressure
𝑤 = −𝑃∆V
❖The negative sign associated with PV work done indicates that the
system loses energy
❖If the volume increases at constant pressure ∆𝑉 > 0 , the work
done by the system is negative
❖Indicating that a system has lost energy by performing work on its
surroundings

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Work and Chemical Reactions
❖If the volume decreases ∆𝑉 < 0 ,the work done by the system is
positive

❖Which means that the surroundings have performed work on the

system

❖thereby increasing its energy

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An Example of Work Performed by a
Reaction

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Enthalpy
❖The enthalpy of a system is defined as the sum of its internal
energy 𝑈 plus the product of its pressure 𝑃 and volume 𝑉
𝐻 = 𝑈 + 𝑃𝑉
❖Internal energy, pressure, volume and enthalpy are state of
function
❖If a chemical change occur at constant pressure (for a given P, ∆𝑃 =
0), the change in enthalpy ∆𝐻 is
∆𝐻 = ∆ 𝑈 + 𝑃𝑉 = ∆𝑈 + ∆PV = ∆𝑈 + 𝑃∆𝑉

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 Enthalpy
❖Substituting 𝑞 + 𝑤 for ∆𝑈 and −𝑤 for 𝑃𝑉
∆𝐻 = ∆𝑈 + 𝑃𝑉 = 𝑞𝑝 + 𝑤 − 𝑤 = 𝑞𝑝
❖Subscript p is to indicate the process occur at constant pressure
❖At constant pressure, ∆𝐻 of the system, defined as 𝐻𝑓𝑖𝑛𝑎𝑙 − 𝐻𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑠 is
equal to the heat gained or lost
∆𝐻 = 𝐻𝑓𝑖𝑛𝑎𝑙 − 𝐻𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝑞𝑝
Enthalpy is a state of function, the magnitude of ∆𝐻 is depend on only the
initial and the final states, not on the path taken.

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