Section 3 Energetics
Section 3 Energetics
Section 3 Energetics
Name: ______________________________
Class: _______________
Class No.: ____________
In exothermic reactions:
Energy needed for bond breaking < Energy released in bond forming
(in the reactants) ( in the products)
∴Heat is released to the surroundings, so the temperature ___________.
In endothermic reactions:
As the solute is dissolved in a large amount of excess of solvent, further addition of solvent
produces no further enthalpy changes.
Example 2
Given that the standard enthalpy change of formation of ethanol is –278 kJmol–1, we can write
the thermochemical equation as follows:
1
2C(graphite) + 3H2(g) + O2(g) → C2H5OH(l) ΔHθf = –278 kJmol–1
2
It should be noted that the enthalpy change of formation of an element is zero (對於一元素
而言,其生成焓變必然是 0。)
Example 3
Write thermochemical equation for the following compounds:
(i) CaCO3(s) ΔHfθ = –1207 kJmol–1
(ii) H2SO4(l) ΔHfθ = –811 kJmol–1
(iii) H2O(l) ΔHfθ = –285.8 kJmol–1
Example 4
Write thermochemical equation for the standard enthalpy change of combustion of the
following substance.
(i) Benzene, C6H6(l) ΔHcθ = –3273 kJmol–1
(ii) C12H22O11(s) ΔHcθ = –5644 kJmol–1
(iii) Propane, C3H8(g) ΔHcθ = –2220 kJmol–1
Note that all enthalpies of combustion must have a negative sign since combustion is
exothermic. (由於燃燒反應是放熱的,所以任何燃燒焓變必定是負值。)
Different standard enthalpy changes may refer to the same equation, for example:
C(graphite) + O2(g) → CO2(g) ΔHθ = –393.5 kJmol–1
The above standard enthalpy change can be a standard enthalpy change of
_____________ of ____________ or standard enthalpy change of ______________
of ______________.
B. Experimental determination of enthalpy changes by calorimetry
Polystyrene cup is used since its heat capacity is low (∴absorb less heat energy) and is a
good insulator (∴↓heat loss).
(發泡膠的比熱容量低,吸收熱能較少,故此是合適的絕緣體。)
Vacuum flask (真空瓶): an even more accurate set-up which can further minimize heat loss
General Procedures:
1. The initial temperature of an acid and an alkali are recorded respectively.
2. Known and same volume of acid and alkali is added to the calorimeter.
3. The reaction mixture is stirred
4. Temperature is measured at regular intervals (e.g. every 5 cm3 of acid/alkali added)
5. A graph of temperature against volume of acid/alkali added is plotted to find the
maximum temperature.
5. Using the graph, the temperature change is calculated
6. Using the following equation, calculate the heat change of the above reaction:
Heat evolved = (m1c1 + m2c2) ΔT
Where m1 = mass of the solution,
m2 = mass of the calorimeter,
c1 = specific heat capacity of the solution,
c2 = specific heat capacity of the calorimeter
ΔT = temperature change of the reaction
7. Calculate the enthalpy change of the neutralization.
Heat evolved
∆H =
No. of mole of water formed
Specific heat capacity of the solution may Determine the exact specific heat capacity
not be equal to that of water (4.18 Jg-1K-1) of the solutions.
(溶液的比熱容未必等於水的比熱容。)
Heat capacity of the polystyrene cup is Determine the exact heat capacity of the
ignored. polystyrene cup as well.
Thermometer is not precise enough Use a Beckmann thermometer or digital
(溫度計不夠準確) devices for higher accuracy in measuring
temperatures (利用貝克曼溫度計或者電
子儀器,使量度出來的溫度更準確。)
Given: Specific heat capacity of final solution = specific heat capacity of water
= 4.18 Jg-1K-1
Density of final solution = Density of water = 1.0 gcm-3
Procedures:
1. Record the mass of ethanol and the mass of spirit lamp.
2. Record the initial temperature of water in the calorimeter.
3. The spirit lamp is ignited for about 10 minutes.
4. Record the final temperature and the increase in water temperature is calculated.
5. The mass of spirit lamp after the experiment is recorded to find the mass of ethanol used.
6. Using the following equation, calculate the heat change of the above reaction:
Possible errors:
1. Heat is carried away by draughts (氣流把熱能帶走) and never enters the calorimeter.
2. Heat lost from the top and sides of the calorimeter. (熱能從量熱器的頂部及邊緣散失。)
3. Heat energy is used to heat up the beaker rather than water.
4. Incomplete combustion. (不完全燃燒)
Improvements:
1. A lid and polystyrene boards as shields are used to reduce heat loss to the surroundings. (把
量熱器用蓋蓋好,並用發泡膠版圍繞量熱器的四周,減少熱能流失。)
2. Assuming the calorimeter/beaker takes the same increase in temperature, calculate
the heat energy absorbed by the calorimeter/beaker as well.
Example 7
Determine the enthalpy change of combustion of ethanol using the following data:
Mass of spirit lamp before experiment: 53.59 g
Mass of spirit lamp after experiment: 52.80 g
Mass of water in copper calorimeter = 50 g
Mass of copper calorimeter without water = 380 g
Initial temperature of water = 20.0℃ (293K)
Final temperature of water = 42.5℃ (315.5K)
The specific heat capacities of water and copper are 4200 Jkg–1K–1 and 2100 Jkg–1K–1
Example 8
In an experiment, 1.60 g of methanol was burnt and 50.0 g of water was heated up, raising the
temperature by 33.2 oC. Given that the specific heat capacities of water and copper calorimeter
are 4200 Jkg–1K–1 and 2100 Jkg–1K–1 respectively and the mass of the calorimeter is 400 g,
calculate the enthalpy change of combustion of methanol.
(b) State the assumptions (假設) made in calculating the enthalpy change of solution in (a).
1. The heat capacities of polystyrene cup and thermometer are negligible. (發泡膠杯 溫
度計的熱容量可忽略不計。)
2. The specific heat capacity of copper(II) sulphate solution is the same as that of water.
(硫酸銅(II)溶液的比熱容量和水的比熱容量值相等。)
3. The density of copper(II) sulphate solution is the same as that of water (1.0 g cm -3).
(硫酸銅(II)溶液的密度和水的密度相等。)
4. Anhydrous copper(II) sulphate dissolves in water quickly such that heat loss to the
surroundings can be negligible (無 水 硫 酸 銅 (II)於 水 中 快 速 溶 解 , 故 此 溶 解 時 的
熱能流失小至可被忽略。).
5. Further dilution of the solution would cause no further heat change.
(c) Indicate the three sources of error in this experiment and suggest how these errors could be
minimized.
Any three of the following:
Possible errors: Improvement:
Heat loss from the system to the Replace the polystyrene cup with a vacuum
surroundings due to conduction, flask calorimeter.
convection and evaporation.
Specific heat capacity of copper(II) Determine the exact specific heat capacity of
sulphate may not be equal to that of water. the copper(II) sulphate solution.
Heat capacity of the polystyrene cup is Determine the exact heat capacity of the
ignored. polystyrene cup as well.
Thermometer is not precise enoughUse a Beckmann thermometer or digital
devices for higher accuracy in measuring
temperatures
Anhydrous copper(II) sulphate may have Gently heat the sample in an oven for several
absorbed moisture from air (實 驗 中 無 水 hours and keep it in a desiccator (乾燥皿).
硫酸銅(II)可能會吸收空氣中的濕氣。).
Example 9
To find the enthalpy change of these reactions, we can apply Hess’s Law ( 赫 斯 定 律 ),
which was formulated by Germain Hess (1802 – 1850), a Russian Chemist.
Hess’s law of constant heat summation:
The total enthalpy change accompanying a chemical reaction is
independent of the route by which the chemical reaction takes place.
(化學反應的總焓變,與其所循的途徑是無關的。)
Which means,
The standard enthalpy change of a reaction depends on only the
difference in standard enthalpy between the reactants and the
products but not on the route of the reaction.
Hess’s law is actually the natural consequence of the law of conservation of energy.
As shown in the following figure, the conversion from X to Y can proceed in two
different routes:
Route 1: Direct conversion, enthalpy change = ΔH1.
Route 2: Indirect route (X → A → B → Y), enthalpy change =ΔH2+ΔH3+ΔH4.
ΔH3
A(s) B(s)
ΔH2 ΔH4
X(s) Y(s)
ΔH1
By Hess’s Law: ΔH1= ΔH2+ΔH3+ΔH4
Enthalpy cycle / Born-Haber cycle: Relate the various equations involved in a reaction
( 把 反 應 中 所 涉 及 的 不 同 方 程 式 連 繫 起 來 。 ). Again, take the oxidation of
C(graphite) to CO2(g) as an example:
Example 11
The chemical equation for the formation of MgCO3 from its constituent elements is as follows:
3
Mg(s) + C(graphite) + O2(g) → MgCO3(s)
2
(a) Suggest two reasons on why the enthalpy change of formation of MgCO3(s) cannot be
determined directly.
(b) Calculate the enthalpy change of formation of MgCO3(s) by using the following data:
Mg(s) +2H+(aq) → Mg2+(aq) + H2(g) ΔH 1 = –434 kJmol–1
MgCO3(s) + 2H+(aq) → Mg2+(aq) +H2O(l) + CO2(g) ΔH 2 = –44 kJmol–1
C(graphite) + O2(g) → CO2(g) ΔH 3 = –394 kJmol–1
1
H2 + O2(g) → H2O(l) ΔH 4 = –286 kJmol–1
2
Example 12
It is impossible to measure the enthalpy change of hydration of magnesium sulphate because
this process is very slow and cannot be controlled. Therefore, this enthalpy change is usually
determined indirectly by measuring the enthalpy change of solution of two related solids.
Experiment A
3.01 g of anhydrous magnesium sulphate were added to 50.0 cm3 of water in a polystyrene cup
and the solution stirred to dissolve the solid as quickly as possible, there was a maximum rise in
temperature of the solution by 11.0℃.
Experiment B
6.16 g of magnesium sulphate-7-water were added to 50.0 cm3 of water in a polystyrene cup and
the solution stirred to dissolve the solid as quickly as possible, there was a maximum fall in
temperature of the solution by 1.5℃.
(a) Calculate the enthalpy of solution of anhydrous magnesium sulphate.
(b) Calculate the enthalpy of solution of magnesium sulphate-7-water.
(c) Calculate the enthalpy change of hydration (水合焓變) of magnesium sulphate.
(d)
Example 13
From calorimetric measurements, the standard molar enthalpies of combustion at 298K for
Graphite = –393.5 kJmol–1
Hydrogen = –285.8kJmol–1
Ethanol = –1371 kJmol–1
Calculate the standard molar enthalpy of formation for ethanol at 298K.
Note: Actually there exists a short cut in calculating ΔH. Read the next example:
Example 14
Calculate the standard enthalpy change for the reaction
2H2S(g) + SO2(g) → 3S(s) + 2H2O(l)
Using only the standard heat of formation data:
Compound ΔHθf /kJmol–1
H2S(g) –20.6
SO2(g) –296.9
H2O(l) –285.9
Enthalpy
Example 16
By using the following thermochemical data, calculate the standard enthalpy change of thermal
decomposition of calcium carbonate. ‘
CaCO3(s) → CO2(g) + CaO(g)
Standard enthalpy change of formation of CaO: –635.1 kJ mol–1
Standard enthalpy change of formation of CO2: –393.5 kJ mol–1
Standard enthalpy change of formation of CaCO3: –1207.6 kJ mol–1
Example 18
Ethanol reacts with phosphorus pentachloride (PCl5) according to the reaction:
C2H5OH(l) + PCl5(s) → C2H5Cl(l) + POCl3(l) + HCl(g)
Calculate the standard enthalpy change of reaction, using the following data:
ΔHθf [C2H5OH (l)] = –277 kJ mol–1
ΔHθf [PCl5 (s)] = –443 kJ mol–1
ΔHθf [C2H5Cl (l)] = –136 kJ mol–1
ΔHθf [POCl3 (l)] = –597 kJ mol–1
ΔHθf [HCl (g)] = –92 kJ mol–1
‘You may read Chapter 6 in your textbook for more examples and exercises’.
Example 19
Given the following information, find the standard enthalpy change of formation of methane.
C(graphite) + O2(g) →CO2(g) ∆ Hc[C(graphite)] = –393.5 kJmol–1
1
H2(g) + O2(g) →H2O(l) ∆ Hc[H2(g)] = –285.8 kJmol–1
2
CH4(g) + 2O2(g) →CO2(g) + 2H2O(l) ∆ Hc[CH4(g)] = –20 kJmol–1
Example 20
Find the standard enthalpy change of formation of butane gas (C4H10(g)).
Given: ΔHθc [C(graphite)] = –393.5 kJmol–1
ΔHθc [H2(g)] = –285.8 kJmol–1
ΔHθc [C4H10(g)] = –2877 kJmol–1
Moreover, it must be noted that ΔH value is not the only factor which determines the
feasibility (可行性) of a chemical reaction.
ΔH is only a state function (狀態函數). It just tells us the current state of the system
(e.g. amount of substance, temperature and pressure), but not the way in which the
system got to that state.
For example, it tells us nothing about the rate of reaction (沒 有 提 供 任 何關 於 反
應速率的資訊。).
Negative ΔH value only tells us that the reaction has the tendency to take place. the
The reactants have to gain a certain amount of energy so that bond breaking can take
place in the reactants. This energy is called the activation energy (Eact)(活 化 能 ), which
represents the energy barrier which the reactants have to overcome before a chemical
reaction can occur (see the figures below).
In other words, a reaction will not occur in the absence of Ea, regardless to the magnitude
or sign of ΔH of the reaction.
This explain why diamond and graphite do not spontaneously decompose into carbon
dioxide although their ΔHc values are highly negative (i.e. “energetically unstable”).
C(diamond) + O2(g) → CO2(g) ΔHθc = –395.4 kJmol–1
C(graphite) + O2(g) → CO2(g) ΔHθc = –393.5 kJmol–1
However, Eact required for the breakdown of the giant covalent network in diamond or
graphite is very high (要拆散金剛石或石墨的巨型共價結構需要極大的活化能。).
The rate will be extremely slow. (∴They are said to be “kinetically stable”.)
The concept of activation energy will be discussed in great detail in Section 5
(Chemical Kinetics).
Also, the kinetic factor also explains why there are some compounds can be formed
endothermically without breaking up into their elements. For example:
Ethyne (C2H2): 2C(graphite) + H2(g) → C2H2(g) ΔHθf = +227 kJmol–1
1 1
Nitrogen monoxide (NO): N2(g) + O2(g) → NO(g) ΔHθf = +90 kJmol–1
2 2
Decomposition of these compounds requires high activation energies
Rate of breakdown is practically unobservable
B. Concept of entropy(熵 )
All substances in nature tend to keep their energy content as low as possible. However,
this rule is not enough to explain whether a process can occur naturally or not.
In fact, there exists another universal rule at the same time:
All substances and particles in the universe tend to be more
disordered (or random). (i.e. having more ways of being arranged)
The state with a high degree of randomness is always favourable in nature
Spontaneous changes involves an increase of randomness
Take melting of ice as an example:
When ice melts, the regularly packed water molecules become free to move in the
liquid state. The system becomes less ordered.
This process occurs spontaneously and endothermically.
Another example is the decomposition of ammonium carbonate:
(NH4)2CO3(s) → 2 NH3(g) + CO2(g) + H2O(g) ΔHθ = + 68 kJ mol–1
Entropy increases
Entropy of solid < Entropy of liquid << Entropy of gas
A perfect crystal at temperature zero K (i.e. absolute zero) has perfect order and zero
entropy (which is actually the Third Law of Thermodynamics). As the substance is
heated, the entropy increases.
Heating increases the motion of particles and therefore the degree of disorder.
Entropy can also be increased by providing more space (i.e. increasing volume) into
which particles can spread.
The entropy added can be described by the following equation:
Q
ΔS = (*)
T
Where Q is the heat absorbed and T is the absolute temperature (in K).
ΔS = S final – S initial (∆ S = S 最終 – S 起始 )
ΔS can be used to indicate the relative degree of disorder of the system. For example:
1. Positive entropy: ΔS = S final – S initial = +ve
e.g. 1 Ice → Water
(Lower entropy) (Higher entropy)
Water molecules in liquid water have more freedom to move than in ice
∴ ΔS = Swater – Sice > 0
Example 21
Predict whether the following changes or chemical reactions involve an increase or a decrease in
entropy. Explain your prediction as well.
(a) Dissolving salt in water to form salt solution
(b) Complete combustion of carbon
(c) Condensation of steam on a cold mirror.
(d) Complete combustion of propane
(e) Oxidation of sulphur dioxide to sulphur trioxide.
(f) Polymerization of ethene to form poly(ethene).
(g) Precipitation of chloride ions by adding silver nitrate(V) solution.
(a) Increase. The solid with ordered crystalline structure dissolves to gives ions which
G = H – TS
For the change in the free energy of the system that occurs during a process, Gibbs
suggested that:
ΔG = ΔH – Δ(TS)
⇒ ΔG = ΔH – TΔS (provided that T is constant)
Gibbs’ Derivation:
Given a chemical reaction taking place at constant temperature and pressure.
ΔHSystem = –ΔHSurroundings
∆H
The equation (*) on P.26 can be rewritten as ∆S =
T
∆H Surrouding s ∆H system
∴∆S Surrouding s = =− (**)
T T
From the Second Law of Thermodynamics, we have,
By the Second Law of Thermodynamics, the total entropy of the universe is always
increasing (i.e. ΔSUniverse > 0).
ΔG = –TΔSUniverse
∴ At constant temperature and pressure, ΔG < 0 For all spontaneous processes (對
於任何自發進行的反應,其自由能變必為負值。)
Conversely, if ΔG > 0, the process must be non-spontaneous, energy from an
external source is required in order to make it happen. (Note: The reverse of that
process will be spontaneous). (相反,如果反應的自由能變為正值,則該反應
無法自發進行,必須有外界的干預和能量的輸入才能令它發生。但注意其
逆反應則可以自發進行。)
If ΔG = 0, the system is said to be at equilibrium (ΔG = 0 時 , 反 應 達 致 平 衡 ),
neither the forward nor the reverse process is favored (i.e. no net change).
∴At any temperature above 0°C, ice begins to melt (∵ΔG < 0)
The following table summarizes the relationship among the exothermicity (ΔH), entropy
change (ΔS) and spontaneity (ΔG) of a process.
ΔH ΔS ΔG = ΔH – TΔS Result Example
–ve +ve –ve Spontaneous at all Exothermic reactions
temperatures. with production of gases
(e.g. burning of fuels)
0 +ve –ve Spontaneous at all CHCl3 dissolves in CCl4
temperatures. (Here ΔH = 0 since the
intermolecular forces of
the two species are
similar. The reduction of
Gibbs free energy arises
solely from the increase
in entropy.)
+ve –ve +ve Non-spontaneous at all Endothermic reactions in
temperatures (its reverse which the number of
process is spontaneous at all moles of gas molecules
temperatures) decreases
(e.g. photosynthesis)
+ve +ve ΔH < TΔS at high Only spontaneous at high Endothermic reactions in
temperatures temperatures (entropy is which the number of
dominant) moles of gas molecules
+ve +ve ΔH > TΔS at low Non-spontaneous increases
temperatures (e.g. evaporation of a
volatile liquid, thermal
decomposition of metal
carbonate)
–ve –ve ΔH < TΔS at low Only spontaneous at low Exothermic reactions in
temperatures temperatures (exothermicity which the number of
is dominant) moles of gas molecules
–ve –ve ΔH > TΔS at high Non-spontaneous decreases
temperatures (e.g. Haber process*)
*Note: However, the Haber process still has to be carried out at relatively high
Example 23
Consider the following reaction:
NH4Cl(s) + aq. → NH4+(aq) + Cl–(aq) ΔGθ = –6.7 kJ mol–1 ; ΔHθ = + 16 kJ mol–1
Explain why does ammonium chloride dissolve spontaneously under standard conditions even
under standard conditions even though ΔH for the process is positive.
It is because when one mole of NH4Cl(s) is dissolved in water, the solid with ordered
crystalline structure dissolves to gives ions which are randomly distributed in solution.
Thus the entropy of the system increase. (當 氯 化 銨 溶 於 水 時 , 原 本 1 摩 爾 具 有 有 秩
序的晶體結構的氯化銨固體被轉化為 2 摩爾分佈在溶液中、無秩序地運動的離子
所以體系中的熵值增加。)
Under standard condition, the entropy change ΔS is positive so that ΔG can still be
negative according to the relation ΔG = ΔH – TΔS. Hence, even though ΔH for the
process is positive, ammonium chloride can dissolve spontaneously. (雖 然在 標準 條件 下
ΔH > 0,但因為 ΔS > 0,根據公式 ΔG = ΔH – TΔS,ΔG 最終仍然能維持負值 。也
就是說體系中熵值的增加足以抵銷焓(能量)的增加。所以氯化銨能夠自發地溶於
水。)
Example 24
You may organize the points your essay as shown below [Total marks of C.K.: 10]
1. What is thermochemistry? [1]
Thermochemistry: The study concerning the energy changes of chemical reactions.
In thermochemistry, the total energy stored in a substance is called enthalpy (H), and
the energy change of chemical reaction at constant pressure is called the enthalpy
change (ΔH).
When heat is absorbed, the reaction is said to be endothermic. For an exothermic
reaction, heat is released to the surroundings from the reaction.
2. Definition of standard enthalpy changes [2]
Enthalpy changes under standard conditions (must include definition of “standard
conditions”), with appropriate notations. [1]
Any two examples (neutralization, formation, solution or combustion) [0.5@]
3. Description of practical methods to determine ΔH [Max: 3]
Describe any two method you learnt in your lesson notes (with experimental details)
[Max: 2, 1@]
Sources of error and improvement [1]
4. Description of indirect method of measuring ΔH based on Hess‘s law [Max: 3]
State Hess’s Law and its scope of application [1]
Example (e.g. ΔHhyd of a hydrated salt such as MgSO4.7H2O(s)), with calculation
details (e.g. use of Born-Haber cycle) [1]
An additional example [1]
5. Uses of thermochemical data [2, 1@]
Relation between ΔH of equilibrium constant (Kc) of a reaction – The Van’t Hoff
Equation (You will learn this in Section 6)
K2 ∆H 1 1
ln =− − (C is a constant)
K1 R T2 T1
♦ ∆ H is the enthalpy change of reaction; R is the universal gas constant (R =
8.314 JK–1mol–1); T is the temperature in Kelvin.
♦ The effect of temperature change on equilibrium
Energetic stability of a compound
Use of bond enthalpy terms to estimate the enthalpy change of a reaction (You will
learn this in Section 4)
8 – 10 6
7 5
6 4
4–5 3
2–3 2
0–1 1