LESSON 1: ENTHALPY OF A CHEMICAL REACTION

Enthalpy of a Chemical Reaction: Thermochemical Equations

Thermochemistry is the study of energy or heat flow that accompanies a chemical reaction and/or
physical transformations.
A chemical equation that shows the value and direction of heat involved in a reaction is specifically called
a thermochemical equation. It also indicates the physical state of the reactants and products involved
in the reaction.
The amount of heat absorbed or released by a chemical reaction at constant atmospheric pressure is
called enthalpy (H). It is a form of chemical energy. The difference between the enthalpy of the products
and the reactants is called the enthalpy of a reaction (ΔH).
ΔH = Hproducts – Hreactants
An exothermic reaction at constant pressure has a negative change in enthalpy (-ΔH), while
an endothermic reaction at constant pressure has a positive change in enthalpy (+ΔH).

For an exothermic reaction, the heat content of reactants is greater than the heat content of the
products since heat is released. The value of ΔH < 0.

For an endothermic reaction, the heat content of the products is greater than the heat content of
the reactants because heat is absorbed. The value of ΔH > 0.

Take Note:
The change in enthalpy (ΔH) is a state function, which refers to a quantity whose value
depends on the current state of the system and not on what has previously occurred. For example,
the temperature of a sample of water is 25°C. This temperature does not depend on its previous
temperature. Its current value is 25°C. Thus, ΔH being a state function depends on the state of each
reactant and product. To explain further, the value of ΔH for a reaction depends only on the conditions
defining the state of the reactants and products and not on the path it takes from reactants to products.
The heat released or absorbed when a reaction takes place is an important and integral part of
the reaction, and could be indicated in the chemical equation. An equation which shows the heat
involved is called a thermochemical equation.
Consider the exothermic combustion of methane (CH4) into carbon dioxide and water.
CH4 (g) + 2O2 (g) à CO2 (g) + 2H2O (l) ΔH = -890.4 kJ
The thermochemical equation means that 890.4 kJ of heat is released when one mole of
gaseous methane and two moles of oxygen gas combust to form one mole of gaseous carbon dioxide
and two moles of liquid water.

TRY THIS!
Write the thermochemical equation described in the problem below.
When one mole of nitrogen gas (N2) reacts with one mole of oxygen gas (O2), two moles of nitric
oxide (NO) are formed. In the process, 180.5 kJ of heat are required.
Enthalpy is also an extensive property. Its magnitude is proportional to the amount of reactants and
products in the reaction. For example, if the amount of reactants and products in a thermochemical
equation is multiplied by 2, the value of the enthalpy is also multiplied by 2. If multiplied by ½, the enthalpy
is also reduced to half.
original equation: CH4 (g) + 2O2 (g) à CO2 (g) + 2H2O (l) ΔH = -890.4 kJ
multiplied by 2: 2CH4 (g) + 4O2 (g) à 2CO2 (g) + 4H2O (l) ΔH = -1780.8 kJ
multiplied by ½: ½CH4 (g) + O2 (g) à ½ CO2 (g) + H2O (l) ΔH = -445.2 kJ
The standard molar enthalpy of formation (ΔH°f) of a compound is the change in enthalpy
when the compound is formed from its elements under standard conditions (1 atm, 25°C). For this reason,
the enthalpy of formation for an element in its stable form is zero under the same standard conditions.
The standard enthalpy of a reaction (ΔH°rxn) can thus be calculated by subtracting the sum (Ʃ)
of the enthalpies of formation of the products and the sum of the enthalpies of formation of the reactants.
Consider the hypothetical equation,
aA + bB à cC + dD
where a, b, c, and d are the respective coefficients of substances A, B, C, D in the balanced
chemical equation. The sum of the enthalpies of formation of the products is calculated as:
ƩΔH°f (products) = c ΔH°f (C) + d ΔH°f (D)

and for the reactants:

ƩΔH°f (reactants) = a ΔH°f (C) + b ΔH°f (D)
Then, the standard molar enthalpy of the hypothetical reaction is calculated as:
ƩΔH°rxn = ƩΔH°f (products) - ƩΔH°f (reactants)
Sample Problem: Consider the combustion of ethanol (C5H5OH) to produce carbon dioxide and water:
C5H5OH (l) + 3O2 (g) à 2CO2 (g) + 3H2O (g)
The standard molar enthalpies of each of the reactants and products can be obtained from table
1-1. The standard enthalpy of the reaction is therefore:

Table 1-1
ΔH°f of Some Common Substances
Specific Heat Specific Heat
Substance Substance
ΔH°f (kJ/mol) ΔH°f (kJ/mol)
C (graphite) 0 H2O (l) -285.8
CO (g) -110.5 N2 (g) 0
CO2 (g) -393.5 NaCl (s) -411.2
C2H5OH (l) -277.7 NH3 (g) -46.3
CaCO3 (s) -1206.9 NO (g) 90.29
CaO -635.6 NO2 (g) 33.85
Fe2O3 (s) -824.2 N2O (g) 81.56
H2O (g) -241.8 O2 (g) 0
If a reaction is an overall process that can be attained through a series of steps of reactions, then the
enthalpy of this overall reaction can be calculated from the thermochemical equations defining the
reactions leading to it.
This approach can be summarized by Hess’s law, which states that the enthalpy of a sum of a
series of reactions is equal to the sum of the enthalpies of those two reactions. In such cases, the
following rules must be considered:
Rule 1: Enthalpy is an extensive property/state function; it depends on the amount of reactants and
products.
Rule 2: The ΔH for a forward reaction is equal in magnitude but opposite in sign to its reverse reaction.
Rule 3: The ΔH for a reaction is the same whether it occurs in one step or in a series of steps.
Let’s take this example,
we can burn carbon directly to carbon dioxide:
C (s) + O2 (g) à CO2 (g) ΔH = -393.509 kJ
or we can do it in two steps: carbon-to carbon monoxide, then carbon monoxide to carbon dioxide,

Cancel CO because it appears on both sides of the equation.

From this example, the overall change is the net result of a series of steps, and the net value of
ΔH for the overall reaction is just the sum of all the enthalpy changes of the different steps.
Note that in the above reaction the heats of the reaction of the individual steps involved
are added algebraically to obtain the overall heat of the reaction.
Just like enthalpy that measures the amount of heat absorbed or released in a thermochemical
reaction, in our life we also absorb and release our energies to or from someone. as a student, there are
many external pressures that you encounter especially when it comes to This teaches us, therefore, to
be sensitive towards the feeling of our fellow. We need to assess if we could absorb or release our
emotions to someone, especially anger. Just like what Mridul said, “The least enthalpy heat of anger can
evaporate the coldest volume of blood. Be condenser and not an evaporator.” Ephesians 4:32 also tells
us to, “Be kind to one another, tenderhearted, forgiving one another, as God in Christ forgave you.”

Sample Problem1: Using the standard molar enthalpies of formation given, calculate the standard
enthalpy of reaction for the combustion of propane (C3H8) into carbon dioxide and water.
C3H8 (g) + 5O2 (g) à 3CO2 (g) + 4H2O (g)
Substance C3H8 (g) O2 (g) CO2 (g) H2O (g)
ΔH°f (kJ/mol) -104.0 0 -393.5 -241.8
Solution:
ƩΔH°rxn = [3ΔH°f (CO2, g) + 4 ΔH°f (H2O, g)] – [ΔH°f (C3H8, g) + 5ΔH°f (O2, g)]
= [3 (-393.5 kJ) + 4 (-241.8 kJ)] – [(- 104.0kJ) + 5(0)]
= -2,043.7 kJ
Sample Problem 2: The thermochemical equation for the incomplete combustion of carbon into carbon
monoxide is represented as

Compute for the ΔH of the reaction if the overall process above can occur in two steps whose
thermochemical equations are given below:
(1) C (s) + O2 (g) à CO2 (g) ΔH = -393.5 kJ
(2) 2CO (g) + O2 (g) à 2CO2 (g) ΔH= -566.0 kJ
Solution:
The ΔH for the overall reaction can be obtained by applying Hess’s Law. First, equation (1)
needs to be multiplied by 2 since C(s) in the overall equation has a coefficient of 2. Rule 1 must be
observed in doing so.
Second, equation (2) must be reversed since carbon monoxide is in the products side of the desired
chemical equation. As such, Rule 2 must be applied.

By Hess’s law, the ΔH of the overall reaction can be calculated from the ΔH of the two (manipulated)
reactions leading to it. In summary,

Sample Problem 3: Calculate the heat of formation of methane CH4. The equation involved is:
C (s) + 2H2 (g) à CH4 (g) ----> This is the desired equation.
The thermochemical equations for the combustion of these species are:
(1) CH4 (g) + 2O2 (g) à CO2 (g) + 2H2O (l) ΔH = -890.4 kJ
(2) 2H2 (g) + O2 (g) à 2H2O (l) ΔH = -571.5 kJ
(3) C (s) + O2 (g) à CO2 (g) ΔH = -393.7 kJ
Solution:
Note that in the desired chemical equation CH4 is on the product side, this we need to reverse
equation (1). When we do so we also have to reverse the sign of ΔH.

We do not need to do anything with equations (2) and (3) since C (s) and H2 (g) are on the
reactant side. In the desired equation, they are also on the reactants side. So, we add the three
equations, cancelling terms that appear on both sides:

GENERALIZATION
Enthalpy is the amount of heat absorbed or released by a chemical reaction at a constant
pressure. The standard enthalpy of a reaction can be calculated as the difference between the sum of
the standard molar enthalpies’ formation of the products and the reactants. It can also be obtained from
the different thermochemical equations that define the overall reaction by applying Hess’s Law.
To summarize how to calculate the ΔH of a specific reaction:
1. Look for the chemical formulas that appear only once among the equations, and place it in the
right place just as in the desired equation.
2. Note the number of moles of each reactant and product in the desired equation.
3. Manipulate the equations with known ΔH values so that the number of moles of reactants and
products is on the correct sides as in the desired equation. Do not forget to:
• Change the sign of ΔH when the equation is reversed.
• Multiply/ divide the number of moles and ΔH by the same factor.

4. Add the manipulated equations, canceling terms that are common to both sides of the equation
to obtain the desired equation. Algebraically add the ΔH values to get the final ΔH, or change in
enthalpy of the desired equation.
LESSON 2: FIRST LAW OF THERMODYNAMICS AND CALORIMETRY

The First Law of Thermodynamics

Thermochemistry is a branch of thermodynamics, which deals with the interconversion of energy
between two forms: heat and work. The energy of a system changes as a function of heat and work.
According to the law of conservation of energy, energy can neither be created nor destroyed. It
only be transferred between the system and the surroundings. The energy of the system (ΔEsys) and
the energy of the surroundings (ΔEsurr) are related by the following equation:
ΔEsys = - ΔEsurr
The negative sign indicates the flow of energy. As the system releases energy, the
surroundings absorb it. Whatever amount of energy that is lost by the surroundings must be gained by
the system.
The first law of thermodynamics states that in any process, the change in energy of a system is
equal to the heat absorbed (q) by the system and the work (w) done on it.
ΔEsys = q + w
Take note:
The law implies that the net energy flow to or from any system comes in the form of either work
or heat. When work is done on the system, it gains energy and work is denoted as positive (+w). When
the system does the work, it uses up or transfer some of its energy so that work is denoted as negative (-
w). Moreover, the system may also absorb heat for which q is positive (+q), or it may release heat to the
surroundings for which q is negative (-q). Thus, the net change in energy either be positive or negative
depending on the means and direction of the energy transfer involved.
Sample Problem 1: Calculate the change in energy for the following processes. Identify if the process
is endothermic or exothermic.
a) A gas releases 35J of heat as 84J of work was done to compress it.
b) A gas absorbs 48J of heat as it does 72J of work by expanding.

Solution:
a) ΔEsys = (-q) + (+w) = -35J + 84J = 49J (endothermic)
b) ΔEsys = (+q) + (-w) = 48J + (-72J) = -24J (exothermic)

TRY THIS! Answer the following problems:

1. What is the work done by a system when it absorbs 47 J of heat and gain 12 J of energy?
2. How much heat is released by a system when 45 J of work is done on it to decrease its energy
to 23 J?

One technique we can use to measure the amount of heat involved in a chemical or physical process is
known as calorimetry. Calorimetry involves the measurement of the quantity of heat exchanged
between a system and its surrounding.

Calorimetry
The flow of energy (as heat) between the system and its surroundings is measured through
calorimetry. The amount of heat absorbed or released by the system is a function of its change in
temperature.
q = CΔt
Δt = tfinal – tinitial
From the equation, heat and temperature change are related by a proportionality constant referred
to as heat capacity (C),which is the amount of energy needed to increase the temperature of a substance
or material by 1°C. This constant is expressed in the units J/°C. The heat capacity of a substance can
only be determined experimentally through calorimetry. For a pure substance, the heat capacity is equal
to the product of its mass(m) and specific heat (c).
C = mc
Therefore,
q = mcΔt
 The specific heat of a substance is the amount of energy needed to increase the temperature of
one gram of the substance by 1°C. Its unit is J/g•°C.
Specific of Common Pure Substances
Substance Specific Heat (J/g•°C)
H2O(s), Ice 2.11
H2O(l) 4.18
H2O(g), Steam 2.08
CO2(g) 0.843
Cu(s) 0.385
Al (s) 0.897
Fe(s) 0.450
C2H5OH(l) 2.43
The specific heat of a substance is constant. The table lists the specific heat values of some
common substances. Different physical states of the same substance (e.g, water) have different values
of specific heat.
To experimentally determine the heat capacity of a substance, a calorimeter is used.
A calorimeter is an insulator apparatus that contains water or any liquid of known heat capacity. In
calorimetry, the system of interest can be a substance (for which heat of solution or heat of dissociation
is measured) or a chemical reaction (for which heat of reaction or heat of neutralization is measured).
This heat exchange can be mathematically expressed as
qsys = [qcalorimeter – qwater]
In some cases, the calorimeter is an excellent insulator and absorbs only a negligible amount of
heat. Thus, the system is assumed to exchange heat only with the water in the calorimeter, and the
expression is simplified to
qsys = -qwater = – (mcΔt) water
A typical calorimeter used in experimentations is the coffee cup that is good as insulator. A
thermometer is inserted in the cork cover to monitor changes in temperature. A stirrer is sometimes used
to ensure uniform mixing of the contents inside the cup. The thermometer and stirrer are assumed to
have negligible effect on the heat exchange.
Sample Problem 1: How much heat is absorbed by liquid water that weighs 550 grams as it is heated
from 25° C to 95°C?
Solution:
q = mcΔt = (550g)(4.18 J/g•°C)(95°C - 25°C) = 160930 J ≈ 161 kJ
Sample Problem 2: How much heat is released by a 76 gram piece of copper as it cools from 450°C
to 28°C?
Solution:
q = mcΔt = (76g)(0.385 J/g•°C)(28°C - 450°C) = -12348 J ≈ 12.3 kJ
Sample Problem 3: The heat solution of a solid sample was determined using a coffee cup calorimeter
that contains 250 milliliters of water initially at 25°C. As the sample is dissolved in the water, the
temperature of the water decreased to 11°C. What is the heat of solution of the sample? Assume that
the density of water is 1.00g/ml and that the coffee cup is a good insulator. Is the process endothermic
or exothermic?
 GENERALIZATION
The First Law of Thermodynamics states that heat is a form of energy, and thermodynamic
processes are therefore subject to the principle of conservation of energy. This means that heat energy
cannot be created or destroyed. It can, however, be transferred from one location to another and
converted to and from other forms of energy.
Formulas under the First Law of Thermodynamics

ΔEsys = - ΔEsurr

ΔEsys = q + w

Calorimetry is the process of measuring the amount of heat released or absorbed during a
chemical reaction. By knowing the change in heat, it can be determined whether or not a reaction is
exothermic (releases heat) or endothermic (absorbs heat). Calorimetry also plays a large part of everyday
life, controlling the metabolic rates in humans and consequently maintaining such functions like body
temperature.
Formulas under the Calorimetry

q = CΔt
Δt = tfinal – tinitial

C = mc
q = mcΔt
LESSON 3: RATE OF REACTION AND RATE LAW FOR REACTION
Chemical Kinetics is the study of the rate of chemical reactions, including the mechanism by which a
chemical reaction occurs and the different factors that affect it.
Many chemical reactions occur spontaneously at a fast rate. The combustion of gasoline with oxygen is
easily initiated under favorable conditions. The reaction between vinegar and baking soda happens
instantly with accompanying bubble formation. Some reactions, however, take time to happen. The
rusting of iron does not happen instantaneously. The green patina (film) on copper that gives the metal
its antique look takes time to form.
The rate of a reaction can be defined as the change in the concentration of a reactant or product per
change in time. The concentration of a reactant or product is represented in square brackets [ ]. For a
hypothetical chemical equation
aA + bB → cC + dD
where a, b, c, and d are the respective coefficients of substances A, B, C, and D in the balanced chemical
equation.
The rate of a reaction can be expressed as
By convention, a negative sign is attached on the change in the concentration of the reactants, which
underscores the fact that the concentration of the reactants decreases as the reaction proceeds. This
convention maintains the positive sign for the rate.
Consider the balanced equation for the decomposition of the colorless gas dinitrogen pentoxide (N2O5)
into the brown nitrogen dioxide gas and oxygen gas.
2 N2O5 (g) → 4NO2 (g) + O2 (g)
The rate of this reaction may be expressed in terms of the change in concentration of N2O5, NO2, or O2 as

The rate expression shows the relative speed at which the concentration of one species changes with
respect to that of another species. In the example, the rate expression indicates that the formation of
NO2 is twice as fast as the decomposition of N2O5 and four times as fast as the formation of O2.
Sample Problem:
1.Hydrogen peroxide (agua oxygenada, H2O2) is a colorless liquid used as disinfectant and bleach. At
high temperatures, it decomposes easily into water and oxygen.
2H2O2 (aq) → 2H2O (l) + O2 (g)
Write the equation for the rate of reaction based on the concentration of the reactants and products.
Solution:
The rate of a reaction can be defined as the change in the concentration of a reactant or product per
change in time. The concentration of a reactant or product is represented in square brackets [ ]. For a
hypothetical chemical equation
aA + bB → cC + dD
where a, b, c, and d are the respective coefficients of substances A, B, C, and D in the balanced chemical
equation.
The rate of a reaction can be expressed as
By convention, a negative sign is attached on the change in the concentration of the reactants, which
underscores the fact that the concentration of the reactants decreases as the reaction proceeds. This
convention maintains the positive sign for the rate.
Consider the balanced equation for the decomposition of the colorless gas dinitrogen pentoxide (N2O5)
into the brown nitrogen dioxide gas and oxygen gas.
2 N2O5 (g) → 4NO2 (g) + O2 (g)
The rate of this reaction may be expressed in terms of the change in concentration of N2O5, NO2, or O2 as

The rate expression shows the relative speed at which the concentration of one species changes with
respect to that of another species. In the example, the rate expression indicates that the formation of
NO2 is twice as fast as the decomposition of N2O5 and four times as fast as the formation of O2.
Sample Problem:
1.Hydrogen peroxide (agua oxygenada, H2O2) is a colorless liquid used as disinfectant and bleach. At
high temperatures, it decomposes easily into water and oxygen.
2H2O2 (aq) → 2H2O (l) + O2 (g)
Write the equation for the rate of reaction based on the concentration of the reactants and products.
Solution:

TRY THIS!
Express the rate of the following reactions in terms of the change in concentration of the reactants
per products.

N2 (g) + 3H2 (g) → 2NH3 (g)

RATE LAW FOR A REACTION

To have an idea how to answer the question above, take note that the rate of reaction depends
on the concentration of the reactants. Hence, the rate law is an important concept for this matter.
The rate law is a mathematical expression that shows how the rate of reaction depends on the
concentration of the reactants. Considering a general equation
aA + bB à products
The rate law for this reaction is expressed as
rate = k [A]x[B]y
where k is the rate constant (dependent on temperature), and the power of x or y is the order of the
reaction with respect to the reactants. The rate of a reaction is expressed in molar per second (M/s). The
unit of the rate constant varies depending on the rate law expression.
The order of the reaction dictates how the rate responds to variations in the concentration of the
reactant. Reactions have therefore different orders as classified below:
Order of a Reaction
A zero-order reaction (x = 0) has a constant rate that is equal to its rate constant regardless of
the changes in the concentration of the reactant.
rate = k [A]0 = k
The first-order reaction (x = 1), the rate doubles when the concentration of a reactant is doubled.
A quadruple increase in reactant concentration means an increase in four times the original rate. In
general, the rate increases in the same order as the concentration of the reactant.
rate = k [A]1 = k [A]
For the second-order reaction (x = 2), increasing the reactant concentration to twice as much
quadruples the original reaction rate. A triple increase in concentration means a ninefold in increase in
reaction rate.
rate = k [A]2
*Note: The expression for the rate law generally bears no necessary relation to the stoichiometric
coefficients in the balanced equation for the reaction, and must be determined experimentally.
Now the question is, how do we determine the order of the reaction given the initial rates of the
substances in several experiment trials? A step-by-step procedure is stated below as well as examples
on how to determine the order, the rate law and the rate constant of reactions.
Determining the Order of a Reaction: Method of Initial Rates
The rate law for a reaction can be experimentally determined through the method of initial rates.
The technique determines how rate is affected by concentration by comparing the initial rates of a reaction
at different initial concentrations of reactants. To illustrate this, consider the hypothetical reaction
A + B à C
 Obtained from three separate experiments, the following data table shows the initial
concentrations of reactants A and B and their reaction rates.
Initial [A] Initial [B] Initial Rate of
Experiment
(M) (M) Reaction (M/s)
I 0.012 0.0034 1.4 x 10-3
II 0.024 0.0034 2.8 x 10-3
III 0.012 0.0068 5.6 x 10-3
To determine the order of the reaction (x) with respect to reactant A, one must choose two experiments
wherein the concentrations of reactant B are the same. This underscores the principle that the initial
rate of the reaction will not be affected by reactant B and will change only with respect to reactant A.
In the given example, experiments I and II are the suitable choices. As observed, the initial rate
increased two times as the concentration of A was doubled. As explained earlier, this type of relationship
indicates a first-order reaction with respect to reactant A.
Mathematically, the order can be determined using two rate laws:
rate2 = k [A]2x [B]2y_
rate1 k [A]1x [B]1y
Since reactant B should have the same concentration, the equation summarizes into
Applying the equation for reactant A in experiments I and II,
2 = 2x
x=1 (first-order reaction with respect to A)
The same method is applied to determine the order with respect to reactant B. In experiments I
and III, the initial concentrations of reactant A are the sane and thus will not contribute to the change in
the initial reaction rate. From the data, the initial rate increased four times as the concentration of reactant
B was doubled. Setting up the ratio of the two rate equations and solving for x,
4 = 2x
x=2 (second-order reaction with respect to B)
The rate law for the hypothetical reaction A + B à C is therefore written as
rate = k [A][B]2
Note that the reaction is third-order overall reaction. The rate constant (k) can be calculated from the rate
law of any of the experiment runs. Using experiment I, k is calculated as
rate = k [A]I [B]I2
k = rate1__ = 1.4 x 10-3 M/s_____
[A]I [B]I2 (0.012 M) (0.0034 M)2
= 1.0 x 104/M2 s

Sample Problem 1:
Chloroform (CHCl3) is a known anesthetic. It is also used to produce the refrigerant carbon tetrachloride
(CCl4) according to the reaction
CHCl3 (g) + Cl2 (g) à CCl4 (g) + HCl (g)
Several experiments obtained the following data:
Initial [CHCl3] Initial [Cl2] Initial Rate of
Experiment
(M) (M) Reaction (M/s)
I 0.0011 0.014 2.60 x 10-4
II 0.0011 0.028 5.20 x 10-4
III 0.0022 0.028 2.08 x 10-3
IV 0.0022 0.014 1.04 x 10-3
Write the rate law expression for the reaction. Calculate the rate constant.
Solution:
To determine the order of the reaction with respect to CHCl3, experiments II and III will be used
since the concentration of Cl2 is constant in these two runs. Based on the results, as the concentration
of CHCl3 is doubled, the rate increases four times. This indicates that the rate is second-order with
respect to CHCl3. To show the mathematical solution,
rateIII = k [CHCl3]IIIx [CL2]IIIy_
rateII k [CHCl3]IIx [Cl2]IIy
Since [CL2]III = [CL2]II,
Applying the principle of logarithm,
To find the order with respect to Cl2, take experiments I and II with similar concentrations of CHCl3.
When the concentration of Cl2 is doubled, the rate also doubles, indicating that the rate is first-order with
respect to Cl2. Thus, the rate law expression for the reaction can be written as
rate = k [CHCl3]2 [Cl2]
The reaction is third-order overall. Using the data from experiment I, the rate constant is
k= rate_____
[CHCl3]2 [Cl2]
= 1.5 x 104/M2 s
Alternatively, experiments I and IV can also be used to determine the order with respect to CHCl3,
and experiments III and IV for the rate order with respect to Cl2. Both methods should give the same
results.

TRY THIS!
Given the experimental data, find the rate law expression and the rate constant for the reaction:
NO (g) + NO2 (g) + O2 (g) à N2O (g)
Initial [NO] Initial [NO2] Initial [O2] Initial Rate of
Experiment
(M) (M) (M) Reaction (M/s)
I 0.10 0.10 0.10 2.1 x 10 -2
II 0.20 0.10 0.10 4.2 x 10 -2
III 0.20 0.30 0.20 1.26 x 10 -1
IV 0.10 0.10 0.20 2.1 x 10 -2

GENERALIZATION
The rate of a reaction is the change in the concentration of a reactant or a product with change in time. The rate
of this reaction may be expressed in terms of the change in concentration of N 2O5, NO2, or O2 as
The rate law expresses how reaction rate varies with the concentration of the reactants. The order of the
reaction indicates the magnitude by which the rate changes with change in concentration. The rate law for the
hypothetical reaction A + B à C is therefore written as
rate = k [A][B]2
To determine the rate law from the experimental data, the procedures are as follows:
1. Identify two experiments in which the concentration of one reactant changed while the other concentration
of the other reactant (s) did not change;
2. Determine how the reaction rate changed in relation to the change in reactant concentration; and
Repeat the process using another set of data in which the concentration of the first reactant did not change while
the concentration of the other one changed.
LESSON 4: ENTROPY, FACTORS THAT INFLUENCE ENTROPY, AND STANDARD
MOLAR ENTROPY
Entropy
Entropy is a measure of molecular randomness. A solid with a rigid structure has low entropy.
Gases whose molecules are in constant random motion in various directions are described to have high
entropy. So, entropy focuses on how order a certain molecule is. Just like the idea of Sagario (2020) as
she states that “In everyday tasks, aiming for an order is what we strive since having things in order allow
us to achieve our objectives.” Generally, randomness of molecules increases the value of its entropy.
Like enthalpy, entropy is a state function; it only depends on the initial and final states of a system.
It does not take into consideration how the final state was attained.
A positive ∆S indicates an increase in randomness of a system; a negative ∆S indicates a
decrease in randomness.
Factors that Influence Entropy
A change in temperature can result in change in entropy. Just like in life, we need to learn to
adapt to any change and know what causes that change in our plans in life. Raising the temperature of
a system increases the average kinetic energy and the freedom of motion of the particles in the system;
thus, increasing the entropy of the system. Conversely, lowering the temperature of the system will lead
to a decrease in entropy. This implies that if the temperature is reduced indefinitely, a system will reach
a condition with zero entropy. This is what the third law of thermodynamics states—that a perfectly
ordered pure crystalline solid at zero Kelvin will have zero entropy.
Chemical reactions that produce higher number of product particles than that of reactant particles are
usually spontaneous. The increase in the number of particles consequently lead to more disorder in the
system and thus its increased entropy.
Consider the spontaneous decomposition of calcium carbonate (CaC03). For every mole of
CaCO3 used, two moles of products are produced.

Spontaneous
Chemical reactions with fewer product particles than the reactants are are described to have negative
entropy and are thus non-spontaneous. Such is the case for ammonia (NH3) production.

Non-Spontaneous
The change in entropy, however, is affected not only by
temperature and number of particles. The graph of entropy
versus temperature (figure 5-2) shows a slow and steady
increase in entropy of a solid substance. At this solid phase
range, the vibrational energy of the particles steadily increases.
Once the melting point of the substance is reached, its entropy
suddenly shoots up. At this condition, the liquid particles are
more free to move than in the solid phase. Aside from
vibrational motion, the liquid particles can have rotational and
translational (i.e., different directions) movements at this stage.
When all solid particles are liquefied, the entropy of the system
returns to a steadily increasing pattern. Once the boiling point
of the. substance is reached, entropy abruptly increases. At
this state, the gas particles are much more free to move.

This general trend is observed for all substances: a steady increase in entropy as the temperature
is raised for a particular phase, then an abrupt increase once the temperature for phase changes is
released.
Sample Problems:
1. Predict the sign of the change in entropy for the following processes:
2. Freezing water
Answer: Entropy change will be negative
2.Heating liquid water to its boiling point
Answer: Entropy change will be positive
1. Predict which substance in each pair has the higher entropy and justify your answer.
2. 1 mol of NH3(g) or 1 mol of He(g), both at 25°C
Answer: Both substances are gases at 25°C, but one consists of He atoms and the other consists
of NH3 molecules. With four atoms instead of one, the NH3 molecules have more motions available,
leading to a greater number of microstates. Hence, we predict that the NH3 sample will have the higher
entropy.

TRY THIS!
1. 1 mol of Pb(s) at 25°C or 1 mol of Pb(l) at 800°C
2. Melting of lead metal at room temperature

Standard Molar Entropy

The standard molar entropy (S˚) of a substance is the entropy of one mole of a substance at
the standard condition (1 atm and 25 ˚C). Note that unlike enthalpy, the standard molar entropy of
substances in their elemental form is not zero; those of pure substances are always positive values (S˚
≥ 0).
As a state function, the standard entropy of reaction ( ∆S˚) can be calculated from the difference
between the standard molar entropies of the products and the reactants involved in the reaction.
∆S˚= ∑S˚ (product) - ∑S˚ (reactants)
For the general reaction:
aA + bB → cC + dD
where a, b, c, and d are the coefficient of the substances in the balanced equation, the standard entropy
of the reaction is calculated as:
∆S˚= ∑S˚ (product) - ∑S˚ (reactants)
= [ cS˚ (C) + dS˚ (D)] - [ aS˚ (A) + bS˚ (B)]

Sample Problem 1
Consider the decomposition of calcium carbonate, the mineral found in limestone.
CaCO3 (s) → CaO (s) + CO2 (g)
Substance CaCO3 (s) CaO (s) CO2 (g)
S˚ (J/ mol.K) 92.9 39.8 213.6
The ∆S is the obtained from the S˚ values of the reactants and products.
∆S˚ = [ S˚ (CaO) + S˚ (CO2)] – [S˚ (CaCO3)]
∆S˚= [ (1mol) (39.8 J/mol. K) + (1mol) (213.6 J/mol. K) – [(1 mol) (92.9 J/mol. K) --> cancel similar units here
∆S˚ = (39.8 J/ K + 213.6 J/K) − 92.9 J/ K
∆S˚ = 160.5 J/K
The decomposition of CaCO3, gives a positive ∆S˚ , which means that the system is in a more random
state under standard conditions than when CaCO3 is formed (reverse reaction

Sample Problem 2
Calculate ΔS° for the following reaction.
H2(g) + I2(s) → 2HI(g)
Substance H2(g) I2(s) HI(g)
S˚ (J/ mol.K) 130.6 116.7 206.3
Using the equation for the standard entropy of reaction, solve for the ∆S˚
∆S˚ = [ S˚ (HI)]– [S˚ (H2) + [S˚ (I2)]
∆S˚ = [ (2mol) (206.3J/mol.K) ] – [ (1mol) (130.6 J/mol.K) + (1mol) (116.7 J/mol.K) ]
∆S˚ = [ 412.6 J/K] – [ 247.3 J/K ]
ΔS° = +165.3 J/K

Sample Problem 3
The Haber process for the industrial synthesis of ammonia is another process that involves gaseous
species.
N2 (g) + 3 H2 (g) → 2NH3 (g)
Substance N2 (g) NH3 (g) NH3 (g)
S˚ (J/ mol.K) 191.5 130.6 192.3
The ∆S˚ is obtained using the following equation
∆S˚= [ 2S˚ (NH3)]– [S˚ (N2) - [3S˚ (NH3)]
∆S˚= [ (2mol) (192.3 J/mol.K) ] – [ (1mol) (191.5 J/mol.K) + (3 mol) (130.6 J/mol.K) ]
∆S˚ = [ 384.6 J/K] – [ 583.3 J/K ]
∆S˚ = -198.7 J/K
TRY THIS!
1. Calculate ∆S˚ for the reaction.
SO2(s) + NO2(g) —> SO3(g) + NO(g)
Given:
S°(J/mol.K): 248.5 240.5 256.2 210.6

GENERALIZATION
Entropy is a thermodynamic quantity that is a measure of how spread out or dispersed the energy of a system
is among the different possible ways that system can contain energy. It is a quantity that is generally used to
describe the course of a process, that is, whether it is a spontaneous process and has a probability of occurring in
a defined direction, or a non-spontaneous process and will not proceed in the defined direction, but in the reverse
direction.
At high enough temperature, the spontaneous change is from Solid Liquid Gas; gas is more random than
liquid and liquid is more random than solid. There is an increase in entropy (S) of the system by going from solid to
liquid to gas.
Entropy is a state function; it only depends on the initial and final states of a system. It does not take into
consideration how the final state was attained. A positive ∆S indicates an increase in randomness of a system; a
negative ∆S indicates a decrease in randomness.
The standard entropy of reaction ΔS° is given by the difference in standard entropies between the products
and the reactants. The standard entropy values of compounds have been measured in J/K mol. To calculate the
ΔS° (which is the ΔSsys), the values may be found in the Thermodynamic Data Table. Thermodynamic tables have
absolute entropy of substances at 25°C and 1atm. Remember, the greater the value of ΔS then the greater is the
increase in the randomness of the system.
Formula:

∆S˚= ∑S˚ (product) - ∑S˚ (reactants)

LESSON 5: SECOND LAW OF THERMODYNAMICS
The Second Law of Thermodynamics
The thermodynamic arrow of time (entropy) is the measurement of disorder within a system.
Denoted as ΔS, the change of entropy suggests that time itself is asymmetric with respect to order of an
isolated system, meaning: a system will become more disordered, as time increases.
The laws of thermodynamics describe the relationships between thermal energy, or heat, and
other forms of energy, and how energy affects matter. The First Law of Thermodynamics states that
energy cannot be created or destroyed; the total quantity of energy in the universe stays the same.
The Second Law of Thermodynamics is about the quality of energy. It states that as energy is
transferred or transformed, more and more of it is wasted. The Second Law also states that there is a
natural tendency of any isolated system to degenerate into a more disordered state.
The second law of thermodynamics explains the relationship between entropy changes and
spontaneity of a process. The changes in this law of thermodynamics are relatable to life such that we
need to learn to adapt to any change and know what causes that change in our plans in life, because as
they say, change is inevitable. Sometimes, we do not have a choice but to go along with it and be strong
and resilient and cling to our almighty God. As the book of Lamentations 3:21-28, “Yet this I call to mind
and therefore I have hope: Because of the Lord’s great love we are not consumed, for his compassions
never fail. They are new every morning; great is your faithfulness.”
In relation to this chemistry concept, it states that for any spontaneous process, there is a net
increase in the total entropy of the system and its surroundings. This net entropy change of the process
is represented as ΔSuniv.
ΔSuniv = [ ΔSsys + ΔSsurr] > 0

Thus, even if ΔSsys is negative, the process can be spontaneous if ΔSsurr is positive and has a
greater magnitude than ΔSsys. If the system is a chemical reaction, ΔSsys is simple ΔS˚ of the reaction
calculated from the S˚ values of the reactants and products. Calculating the ΔSsurr, however, requires
recalling the first law of thermodynamics, which states that energy is exchanged between the system and
its surroundings in the form of heat and work. The entropy change in the surroundings is directly
proportional to the enthalpy changes of the reaction and inversely proportional to the absolute
temperature (in Kelvin) of the surroundings. In mathematical expression,
ΔSsurr = - Δ Hrnx
T
Sample Problem 1: Compute for the total entropy change (ΔSuniv) in the oxidation of metallin ion into
ferric oxide (Fe2O3) under standard conditions. Determine the spontaneity of the process at these
conditions.
4 Fe + 3O2 → 2 Fe2O3
Solution:
First, ΔS˚ of the reaction is obtained from the S˚ values of the reactants and products.
Substance Fe O2 Fe2O3
S˚ (J/ mol.K) 27.3 205.0 87.4

The ΔH˚rnx is calculated from the standard molar enthalpies of formation (ΔH˚f) of the reactants
can products. Since ΔH˚f for elemental substances is zero and that for Fe2O3 is – 824.2 kJ/mol.
* Notice that the change in entropy of the reaction is negative, but the entropy change in the surroundings is large
enough such that the total entropy of the process is positive. This indicates that the oxidation of iron is a
spontaneous process at standard conditions.

Sample Problem 2: Calculate the entropy change in the surroundings of the reaction shown below at
25 ˚C and 1 atm. ( ΔH= - 566 kJ)
2CO + O2 → 2CO2
Note:
* Convert the given kJ into J = -566 kJ ≈ -566000 J
* Temperature= 25 ˚C + 273 = 298 K

Solution:
ΔSsurr = - ΔH˚rnx / T
= - (-566000 J)
298 K
ΔSsurr = + 1899 J/K

Sample Problem 3: Calculate the total entropy change for the decomposition of hydrogen peroxide
(H202). Is the reaction spontaneous or not?
2 H2O2 → 2 H2O + O2
Substance H2O2 H2O O2
S˚ (J/ mol.K) 109.6 69.9 205.0
ΔH˚f (kJ/mol) -187.8 -285.8 0

Solution:

TRY THIS! Answer the problem below:

Applying the procedure for calculating the ΔSsys and ΔSsurr to the synthesis of ammonia: Is the
reaction spontaneous at 25°C?
N2 (g) + 3 H2 (g) —> 2 NH3 (g) ΔH°rxn = - 92.6 kJ/mol

GENERALIZATION
The Second Law of Thermodynamics deals with entropy. It tells whether a process or chemical reaction
can occur. The connection between entropy and the spontaneity of a reaction is expressed by the second law of
thermodynamics.
It states that: “The entropy of the universe increases in a spontaneous process and remains
unchanged in an equilibrium process.”
Because the universe is made up of the system and the surroundings, the entropy change in the universe
(ΔSuniv) for any process is the sum of the entropy changes in the system (ΔSsys) and in the surroundings (ΔSsur).
ΔSuniv = ΔSsys + ΔSsur > 0 Process is spontaneous
ΔSuniv = ΔSsys + ΔSsur = 0 Process tends not to occur; equilibrium is attained
ΔSuniv = ΔSsys + ΔSsur < 0 Reverse process occurs spontaneously

Formula:
1. ΔSuniv = [ ΔSsys + ΔSsurr]
2. ΔSsurr = - ΔH˚rnx / T
LESSON 6: REVERSIBLE CHEMICAL REACTIONS

Chemical Equilibrium
An example in our atmosphere is the equilibrium between nitrogen dioxide, NO2, and dinitrogen
tetroxide, N2O4. Most of the NO2 in the atmosphere comes from automobiles. It also forms from the
breakdown of N2O4 in an equilibrium reaction. While NO2 is being formed from N2O4, N2O4 is being
formed from NO2 by the reverse process:
N2O4 à 2NO
2NO2 à N2O4
The NO2 is a brown gas, while the N2O4 is colorless. The brown color of smog is partially due to
the presence of NO2. Without the equilibrium that exists between NO2 and N2O4, the smog would appear
significantly darker. In this section, we'll look at factors that influence both reaction rates and the
equilibrium in reactions such as these.
Forward reaction: N2O4 → 2NO
Reverse reaction: 2NO2 → N2O4

This state of equilibrium, where the forward and reverse reactions occur at the same rate, is
represented using an equilibrium arrow (⇌)
N2O4 (g) ⇌ 2NO2 (g)
When any chemical reaction reaches the equilibrium state, the rates of the forward and reverse
reactions are equal; there is no net change in the concentrations of reactants and products. Reactions
that reach a state of equilibrium are reversible reactions. A true equilibrium exists in a closed system,
where neither reactants nor products can enter or leave.

The conversion of N2O4 to NO2 is a reversible reaction and reaches a state of chemical equilibrium.
(A and B) These show the system before equilibrium. (C and D) These show the system after equilibrium.
At equilibrium, the numbers of N2O4 and NO2 molecules do not change. However, N2O4 is still being
converted to NO2, while NO2 is converted back to N2O4 at an equal rate.
Take note:
When a reaction reaches equilibrium, amounts of reactants and products may be about equal.
More often, however, one or the other predominates: either a large amount of reactants and small amount
of products, or a small amount of reactants and a large amount of products.
When the concentration of reactants at equilibrium is large relative to the concentration of
products, we say the equilibrium favors reactants. When the concentration of products at equilibrium is
large relative to the concentration of reactants, we say the equilibrium favors products.

The Equilibrium Constant

Let’s examine a chemical system at the macroscopic and molecular levels to see how equilibrium arises
and then consider some quantitative aspects of the process:
1. A macroscopic view of equilibrium. The system we’ll consider is the reversible gaseous reaction
between colorless dinitrogen tetroxide and brown nitrogen dioxide:
N2O4 (g; colorless) ⇌ 2NO2 (g; brown)
As soon as we introduce some liquid N2O4 (bp = 21°C) into a sealed container kept at
200°C, it vaporizes, and the gas begins to turn pale brown. As time passes, the brown darkens,
until, after less than 30 seconds, the color stops changing. The first three photos show the color
change, and the last photo shows no further change.
2. A molecular view of equilibrium. On the molecular level, as shown in the blowup circles, a
dynamic scene unfolds. The N2O4 molecules fly wildly throughout the container, a few splitting into two
No2
As time passes, more N2O4 molecules decompose and the concentration of NO2 rises. As
the number of N2O4 molecules decreases, N2O4 decomposition slows down. At the same time,
increasing numbers of NO2 molecules collide and combine, and re-formation of N2O4 speeds up.
Eventually, the system reaches equilibrium: N2O4 molecules are decomposing into
NO2 molecules just as fast as NO2 molecules are combining into N2O4.
Thus, at equilibrium, reactant and product concentrations are constant because a change
in one direction is balanced by a change in the other as the forward and reverse rates become
equal:
At equilibrium: ratefwd = raterev

3. A quantitative view of equilibrium a constant ratio of constants. Let's see how reactant
and product concentrations affect this At a particular temperature, when the system reaches
equilibrium, we have
ratefwd = raterev
In this reaction system, both forward and reverse reactions are elementary steps, so we
can write their rate laws directly from the balanced equation:
kfwd [N2O4]eq = krev [NO2]2eq
where kfwd and krev are the forward and reverse rate constants, respectively, and the
subscript “eq” refers to the concentrations at equilibrium. By rearranging, we set the ratio of the
rate constant equal to the ratio of the concentration terms:
kfwd = [NO2]2eq
krev [N2O4]eq
The ratio of constants creates a new constant called the equilibrium constant (K):
The equilibrium constant, K, is a number equal to a particular ratio of equilibrium
concentrations of product(s) to reactant(s) at a particular temperature.

4. K as a measure of reaction extent. The magnitude of K is an indication of how far a reaction

proceeds toward a product at a given temperature.
Here are three examples of different magnitude of K:

• Small K (A). If a reaction yields little product before reaching equilibrium, it has a small K; if K is
very small, we may say there is “no reaction”. For example, there is “no reaction” between
nitrogen and oxygen at 1000 K:
N2 + O2 ⇌ 2NO K = 1 X 10-30
 • Large K (B). Conversely, if a reaction reaches equilibrium wth little reactant remaining, it has a
large K; if K is very large, we say the reaction “goes to completion”. The oxidation of carbon
monoxide “goes to completion” at 1000 K:
2CO + O2 ⇌ 2CO2 K = 2.2 x 1022
*To distinguish them in print, the equilibrium constant is represented by a capital italic K,
whereas the temperature unit, the kelvin is a capital roman K. Also, since the kelvin is a
unit, it always follows a number.

• Intermediate K (C). When a significant amounts of both reactant and product are present at
equilibrium, K has an intermediate value, as when bromine monochloride breaks down to its
elements at K:
2BrCl ⇌ Br2 + Cl2 K=5
How can we describe a state of equilibrium mathematically in terms of the relative concentrations of
reactants and products?

Let’s look at the different sets of equilibrium concentrations for a specific reaction to see if we can
determine the relationship between them that will give the same value for all sets of equilibrium
concentrations. We will consider the following reversible reaction:
2HI ⇌ H2 + I2

Table 12.1 shows the concentrations of reactants and products at equilibrium that result when the
reaction is run three times, each time starting with different amounts of reactants and products. The table
also shows the results of three different ways to describe the relative amounts of reactants and products.
Which expression in Table 12.1 gives relatively constant values for the three experiments?
From Table 12.1 we can see that the expression in the last column gives values that are extremely
close in all cases (0.200, 0.201, and 0.199). From these three trials we could calculate an average
constant of 0.200. The expression that gives a constant in Table 12.1 is the product concentrations
multiplied together and divided by the reactant concentration squared. Why is the reactant concentration,
[HI], squared? Does it have anything to do with the coefficient 2 in front of HI in the balanced
equation? YES, it does.
Chemists have studied a variety of reactions under many conditions. They have found that an
expression like that in the last column of Table 12.1 gives a constant (the equilibrium constant, Keq) for
any reaction under conditions of constant temperature. In general, for a reaction with the general form
aA + bB ⇌ cC + dD
the equilibrium constant expression is
Keq = [C]c [D]d
[A]a [B]b
where [A], [B], [C], and [D] are the molar concentrations of the reactants and products at
equilibrium, and the exponents a, b, c, and d are the values of the coefficients in the balanced equation.
The value of the equilibrium constant Keq can be determined when equilibrium concentrations of
reactants and products are known. The value of the equilibrium constant for a specific reaction is always
the same at a specific temperature. If the temperature of the reaction system changes, the value of the
equilibrium constant changes.
Sample problem 1: Let’s write the equilibrium constant expression for the formation of ammonia
from its elements. The balanced equation is
N2 + 3H2 ⇌ 2NH3
The equilibrium constant expression is
Keq = [NH3]2
 [N2] [H2]3
*Remember that when no coefficient appears in the balanced equation, the coefficient is
understood to be 1. We normally leave the exponent 1 out of the equilibrium constant expression.
Suppose we combine N2 and H2 gases in a reaction container at 400 K Figure 12.16 shows the relative
concentrations before the reaction occurs and after the reaction has reached equilibrium. The equilibrium
concentrations of reactants and product are as follows:
[N2] = 0.0600 M
[H2] = 0.180 M
[NH3] = 0.280 M
To calculate the value of the equilibrium constant at 400 K, we substitute these equilibrium
concentrations into the equilibrium constant expression:

The value of the equilibrium tells us about the position of the equilibrium.
• When its value is much greater than 1, there are more products than reactants at equilibrium,
and we say that the position of equilibrium lies to the right. We can see from Figure 12.16 that
the equilibrium concentration of the NH3 product is greater than either one of the reactant
equilibrium concentrations.
• If the value of the equilibrium constant is much less than 1, there are more reactants than
products at equilibrium, and we say that the position of the equilibrium lies to the left.
• If the value of the equilibrium constant is about 1, similar amounts of reactants and
products exist at equilibrium.

Sample Problem 2: Sulfur tetroxide is placed in a reaction container, heated to 130°C, and allowed
to reach a state of equilibrium:
2SO3 ⇌ 2SO2 + O2
The equilibrium concentrations are determined to be
[SO2] = 0.026 M
[O2] = 0.013 M
[SO3] = 0.12 M
a) Write the equilibrium constant expression for this reaction.
b) Calculate the value of the equilibrium constant at 130°C.
c) Describe the position of the equilibrium.
 TRY THIS! Answer the following problems below. Show your complete solution.
Consider the reaction: PCl5 ⇌ PCl3 + Cl2. At a specific temperature, the equilibrium
concentrations were determined to be [PCl5] = 0.20 M, [PCl3] = 0.025 M, and [Cl2] = 0.025 M. a)
What is the value of the equilibrium constant? b) Describe the position of the equilibrium.

ICE tables are composed of the concentrations of molecules in solution in different stages of a
reaction, and are usually used to calculate the K, or equilibrium constant expression, of a reaction (in
some instances, K may be given, and one or more of the concentrations in the table will be the unknown
to be solved for). ICE tables automatically set up and organize the variables and constants needed when
calculating the unknown.

ICE is a simple acronym for the titles of the first column of the table.
• I stands for initial concentration. This row contains the initial concentrations of products and
reactants.
• C stands for the change in concentration. This is the concentration change required for the
reaction to reach equilibrium. It is the difference between the equilibrium and initial rows. The
concentrations in this row are, unlike the other rows, expressed with either an appropriate
positive (+) or negative (-) sign and a variable; this is because this row represents an increase
or decrease (or no change) in concentration.
• E is for the concentration when the reaction is at equilibrium. This is the summation of the initial
and change rows. Once this row is completed, its contents can be plugged into the equilibrium
constant equation to solve for Kc.

The procedure for filling out an ICE table is best illustrated through example
Sample Problem: Use an ICE table to determine Kc for the following balanced general reaction
2X ⇌ 3Y + 4Z
where the capital letters represent the products and reactants. (This equation will be placed
horizontally above the table, with each product and reactant having a separate column.)
A sample consisting of 0.500 mol of x is placed into a system with a volume of 0.750 liters.
At, equilibrium, the amount of sample X is known to be 0.350 mol.
• This statement implies that there are no initial amounts of Y and Z. For the I row of the Y and Z
columns, 0.000 mol will be entered.
• Notice that the initial composition is given in moles. The amounts can either be converted to
concentrations before putting them into the ICE table or after the equilibrium amounts have
been calculated. This example uses moles for the ICE table, and calculates concentrations
later.
Solution:
Kc = [Y]3 [Z]4
[X]2
The equilibrium concentrations of Y and Z are unknown, but they can be calculated using the
ICE table.
Step 1: Fill the given amounts

Reaction: 2X 3Y 4Z
Initial amounts 0.500 mol 0.000 mol 0.000 mol
Change in amount ? ? ?
Equilibrium amount 0.350 mol ? ?

Step 2: Fill the amount of change for each compound

Reaction 2X 3Y 4Z

Initial amounts 0.500 mol 0.000 mol 0.000 mol

Change in amount -0.150 mol +0.225 mol +0.300 mol

Equilibrium amounts 0.350 mol ? ?

 Notice that the equilibrium in this equation is shifted to the right, meaning that some amount of
reactant will be taken away and some amount of product will be added (for the Change row).
The change in amount (xx) can be calculated using algebra:
Equilibrium Amount = Initial Amount + Change in Amount
Solving for the Change in the amount of 2x gives:
0.350mol−0.500mol=−0.150mol
The change in reactants and the balanced equation of the reaction is known, so the change in
products can be calculated. The stoichiometric coefficients indicate that for every 2 mol of x reacted, 3
mol of Y and 4 mol of Z are produced. The relationship is as follows:

Try obtaining the change in Z with this method (the answer is already in the ICE table).
Step 3: Solve for the equilibrium amounts

Reaction 2X 3Y 4Z

Initial amounts 0.500 mol 0.000 mol 0.000 mol

Change in amounts -0.150 mol +0.225 mol +0.300 mol

Equilibrium amounts 0.350 mol 0.225 mol 0.300 mol

If the initial amounts of Y and/or Z were nonzero, then they would be added together with the
change in amounts to determine equilibrium amounts. However, because there was no initial amount for
the two products, the equilibrium amount is simply equal to the change:

Use the same method to find the equilibrium amount of Z. Convert the equilibrium amounts to
concentrations. Recall that the volume of the system is 0.750 liters.

GENERALIZATION
Kinetics and equilibrium are distinct aspects of a
reaction system, and the rate and extent of a reaction are not
necessarily related. When the forward and reverse reactions
occur at the same rate, concentrations no longer change and
the system has reached equilibrium. The equilibrium constant
(K) is a number equal to a particular ratio of product to
reactant concentrations at a certain temperature: K is small if
a high concentration of reactant(s) is present at equilibrium,
and it is large if a high concentration of product(s) is present at equilibrium.
We have the formula for equilibrium constant.
aA + bB ⇌ cC + dD
the equilibrium constant expression is
Keq = [C]c [D]d
[A]a [B]b
LESSON 7: ACIDS AND BASES
Acid and Base Definitions
In the late 1800s, a Swedish doctoral student named Svante Arrhenius proposed a definition
of acids and bases based on his experiments with electrolytes. Because aqueous solutions of
acids and bases conduct electricity, Arrhenius knew that the compounds were forming positive
and negative ions in the solution. Arrhenius proposed that acids and bases produce specific types
of ions that other compounds do not. In the Arrhenius model of acids and bases, an acid in an
aqueous solution produces hydrogen ions, H+, and a base produces hydroxide ions, OH- . For
example, hydrochloric acid ionizes in water to form H+ (aq) and Cl-(aq):

The base sodium hydroxide dissociates when it dissolves in water to form sodium ions and
hydroxide ions:

The Arrhenius model explains how acids and bases neutralize each other. In a neutralization
reaction of HCI and NaOH, for example, the H from the HCI combines with the OH- from NaOH
to produce water:

Although his model does not adequately describe acids and bases as we know them today,
Arrhenius earned the 1903 Nobel Prize in Chemistry because he insisted that the H+(aq) and
OH- (aq) ions are important in acid-base behavior. Because of the simplicity of its definition, the
model is still used when only a brief explanation of acid-base behavior is needed.
The Arrhenius definition of acids and bases is limited by some
fundamental problems. The hydrogen ion, H+, essentially a proton with
an extremely small radius, has a very concentrated positive charge. As a
result, free H+ ions are unlikely to exist in aqueous solution. Instead, they
are associated with surrounding water molecules. Chemists today
normally represent the aqueous H+ ion as H3O+ (aq), the hydronium ion
(Figure 13.4). Another limitation to the Arrhenius model is that it assumes
all bases contain OH- ions, but some do not. Many other ionic
compounds, commonly called salts, have basic properties, such as the
ability to neutralize acids. Examples of salts that are bases are metal
oxides, carbonates, and fluorides. Some molecular compounds that no
group, such as ammonia, NH3, also have basic properties.
In 1923 J. N. Brønsted, a Danish chemist, and T. M. Lowry, a British chemist, independently
proposed a new theory to deal with the limitations of the Arrhenius model. The Brønsted-Lowry
theory defines an acid as any substance that can donate an H+ ion to another substance; it defines
a base as any substance that can accept an H+ ion from another substance. These definitions
include all the Arrhenius acids and bases plus some ions in salts and some molecular compounds
such as ammonia. According to the Brønsted-Lowry theory, when HCI gas dissolves in water, it
donates an H+ to H2O to form hydronium ions and chloride ions:

Note that 1-120 acts as a Brønsted-Lowry base by accepting the H+ from HCI. Ammonia
dissolved in water acts as a Brønsted-Lowry base by the following equation:

In this case, water acts as an acid by donating the H+ to the NH3 molecule. Note that OH-
(aq) ions form, but the —OH group is not present as part of the base initially. Hydroxide ions form
as a result of the Brønsted-Lowry acid-base reaction between NH; and H2O. There are many
organic amines (compounds that contain the —NH2 group) that act as bases in water. An example
is a methylamine, CH2NH2:

Brønsted-Lowry bases also include anions, such as the carbonate ion, CO3 2- which is
found in the compound Na2CO3 used to alter the pH of swimming pool water. When added to
water, Na2C03 first dissociates completely into its ions:
 Brønsted-Lowry acid-base reactions do not always involve water as the acid or base.
Sometimes another substance in the water is better able to give or receive an H+ ion. In the
following reaction, hydrofluoric acid donates an H+ to the carbonate ion base to form fluoride ion
and bicarbonate ion:

Example 13.1: Brønsted-Lowry Acids and Bases

For each reaction, identify Brønsted-Lowry acid-base reactants.

Solution:
The name of HNO3, nitric acid, tells us that it is an acid. However, we can also identify it as an
acid because it donates an H+ to water as shown in the equation. Water accepts H+ from HNO3
to form H3O+(aq), so H2O is the base.

The sulfate ion, (SO4)2-, does not have any hydrogens to donate, so it cannot be the acid. Instead,
it is the base because it accepts H+ to form HSO4-(aq). Water donates the H+, forming OH-(aq),
so H2O is the acid in this reaction.

Methylamine, CH3NH2, acts as a base in water because it accepts an H+ forming CH3NH3+(aq),

Carbonic acid, H2CO3, donates the H+, forming HCO3-(aq), so H2CO3 is the acid in this reaction.
Consider this 13.1

If reaction (c) runs in reverse, which would be Brønsted-Lowry base?

Practice Problem 13.1
For each reaction, identify the Brønsted-Lowry acid and base reactants.

CONJUGATE ACID-BASE PAIRS

When an acid donates an H+ to a base, the two products differ from the reactants by one
H+ ion. The product that forms as a result of gaining an H+ ion is called the conjugate acid of the
base from which it forms. The product that forms as a result of losing an H+ ion is called the
conjugate base of the acid from which it forms. Consider the reaction of hydrogen chloride gas
with water:

In water, the acid, HCI, reacts to form its conjugate base, Cl-(aq). The base, H2O, reacts to
form its conjugate acid, H3O+(aq). The acid reactant and the conjugate base product are a
conjugate acid-base pair. Likewise, the base reactant and the conjugate acid product are a
conjugate acid- base pair. Conjugate acid-base pairs always differ by one H+ ion. The conjugate
acid of a substance has one more H the conjugate base of a substance has one less H+ . The
conjugate base of an acid is what is left after the acid donates an H+ to another substance. The
conjugate base, then, has one less H atom in its formula and a decrease in charge of 1. Given
that a substance reacts as an acid or a base, you should be able to identify its conjugate.
Example 13.2 Conjugate Acids and Bases
Identify the conjugate base for each acid and explain its charge.
Solution:
The conjugate base of HOCI is OCI-. It has one less H atom than the acid and a charge of 1—, one
less than the zero charge on HOCI.

The conjugate base of H2PO4- is HPO42-, which has one less H atom than the acid and a charge
of 2—, one less than the 1— charge on H2PO

The conjugate base of H2O is OH-, which has one less H atom than H2O and a charge of 1—, one
less than the zero charge on H2O.

Consider this 13.2

If the H2PO4- ion acts as a base, what is its conjugate acid?

Practice Problem 13.2

Identify the conjugate acid for each base.

a. F-
b. HCO3-
c. H2O
STRONG AND WEAK ACIDS AND BASES
Jake uses a solution of HCI to lower the pH of pool water which is too basic. One reason
that he uses HCI is that it is a strong electrolyte that ionizes completely in Solution. Some acids
and bases are strong electrolytes, and others are weak electrolytes. An acid or base that is a
strong electrolyte and completely ionizes or dissociates in water is a strong acid or a strong base.
An acid or a base that is a weak electrolyte and only partially ionizes in water is a weak acid or a
weak base.
TABLE 13.1 COMMON STRONG ACIDS
FORMULA NAME
HCL Hydrochloric Acid
HBr Hydrobromic Acid
HI Hydroiodic Acid
HNO3 Nitric Acid
HClO3 Chloric Acid
HClO4 Perchloric Acid
H2SO4 Sulfuric Acid (only one H+ ionizes completely)

Strong Acids
Strong acids ionize completely when dissolved in water. When the strong acid HCI ionizes
in water, the resulting solution consists of only H O , Cl-, and H20. It contains essentially no un-
ionized HCI. Table 13.1 lists the common strong acids.
Some of the strong acids listed in Table 13.1 should be familiar to you. Hydrochloric acid,
HCI, is the acid in your stomach that aids in digestion. It is also the acid that pool maintenance
people like Jake use to wash the plaster of swimming pools. Sulfuric acid, H2SO4, is the acid in
most car batteries, and it occurs in acid rain. Nitric acid, HNO3, also occurs in acid rain.

Strong Bases
Strong bases dissociate completely when dissolved in water. The strong base sodium
hydroxide, NaOH, dissociates completely in water to form Na (aq) and OH (aq). Essentially no
undissociated NaOH(aq) remains. Most of the common strong bases are the ionic hydroxides of
the group IA (l) and IIA (2) metals. Table 13.2 lists the common strong bases. Commercial oven
and drain cleaners contain the strong base sodium hydroxide, NaOH. Sodium hydroxide is also
used in processing paper and in canning olives. Calcium hydroxide, Ca(OH)2, sometimes called
slaked lime, forms when lime, CaO, mixes with water. Calcium oxide is sometimes used to reduce
the acidity levels in garden soil. Magnesium hydroxide, Mg(OH)2, is a strong base used as an
antacid, it is relatively insoluble in water.
Common Strong Bases
Formula Name Formula Name
LiOH lithium hydroxide Mg(OH)2 magnesium hydroxide
NaOH sodium hydroxide Ca(OH)2 calcium hydroxide
KOH potassium hydroxide Ba(OH)2 barium hydroxide
Weak Acids
How do we know if an acid is a weak acid? Any acid that is not a strong acid is a weak acid.
A weak acid does not ionize completely when dissolved in water. An equilibrium forms between a
weak acid and its conjugate base, so both the reactants and the products are present
in the solution. Examples of weak acids are citric acid, malic acid, and acetic acid. They are
commonly found in fruits and other foods. Table 13.3 lists some weak acids and where they
commonly occur.
When a weak acid dissolves in water, usually fewer than 10% of the molecules transfer an
H+ to the water, leaving the conjugate base. The rest remain in the molecular form. The equilibrium
lies far to the left. We use equilibrium arrows (when writing an equation to describe the ionization
of a weak acid such as acetic acid, CH3CO2H, in water:
Common Weak Acids
Formula Name Occurrence
CH3COH acetic acid vinegar, sour wine
H2CO3 carbonic acid soda, blood
H3C6H507 citric acid fruit, soda
used in glass etching and semiconductor
HF hydrofluoric acid
manufacturing
HOCI hypochlorous acid used to sanitize pools and drinking water
HC3H503 lactic acid milk
HCH4O5 malic acid fruit
H2C2O4 oxalic acid nuts, cocoa, parsley, rhubarb
H3PO4 phosphoric acid soda, blood
HCHO6 tartaric acid candy, wine, grapes
Other weak acids that ionize in water are cations which are the conjugate acids of weak bases.
Ammonium ion, NH4+, is an example of a weak acid. It is found in the compound ammonium nitrate,
NH4NO3, which Olivia uses to fertilize her plants. How does NH4NO3 act as an acid? Consider what
happens when NH4NO3 dissolves in water. Like any other soluble ionic compound, it dissociates to its
aqueous cations and anions:

Nitrate ion, NO3-, is the conjugate base of a very strong acid, so it does not behave as a base with
water. The NH4+(aq), however, reacts with water as a weak acid and donates an H+ ion to water:

Weak Bases
A weak base does not completely ionize when dissolved in water. An equilibrium forms
between a weak base and its conjugate acid. Ammonia is a common weak base. The most
common weak bases are organic compounds that contain the amine group (—NH2), such as
methylamine, CH3NH2. Methylamine is a weak base, so we show its ionization in water with
equilibrium arrows:

Other weak bases that ionize in water are anions which are the conjugate bases of weak
acids. Hypochlorite ion, OCI-, is an example of a weak base. It is found in the compound
calcium hypochlorite, Ca(OCl)2, that Jake uses to super chlorinate the water in swimming pools.
How does Ca(OCl)2 act as a base? Consider what happens when Ca(OCl)2 dissolves in water.
Like any other soluble ionic compound dissolved in water, it dissociates to its aqueous cations
and anions:
 The anions that are the conjugate bases of weak acids are typically obtained from ionic
compounds that contain the anion. For example, the hypochlorite ion used in pool sanitation can
come from a variety of compounds, including Ca(OCl) Some pool products contain
sodium hypochlorite, NaOCl, instead. Identifying ionic compounds that behave as weak bases is
relatively straightforward once you identify the anion. If the anion is the conjugate base of a weak
acid, it will typically behave as a base when added to water. For example, sodium acetate,
NaCH3CO2, is a soluble ionic compound that dissociates to give Na+ (aq) and CH3CO2-(aq) ions.
Consulting Table 13.3, we see that acetic acid is a weak acid with the formula CH3CO2H The
acetate ion, CH3CO2-, is the conjugate base of acetic acid, so we can predict that an ionic
compound containing the acetate ion behaves as a weak base. On the other hand, if the anion is
the conjugate base of a strong acid, it will not react as a base with water. For example, NaCl
contains the conjugate base, Cl-, of the strong acid HCI. Conjugate bases of strong acids do not
react with water, so NaCl will not behave as a base.

Table 13.4 lists some common weak bases and where they are found. For those that are ionic
compounds, identify the anion that acts as a base when the compound dissolves in water.

Common Weak Bases

Formula Name Occurrence

NH ammonia Glass cleaners
CaCO3 calcium carbonate Antacids, minerals
Ca(OCI) calcium hypochlorite Chlorine source for swimming pools
CH3NH2 methylamine Herring brine
(CH3)3N trimethylamine Rotting fish

Water as Both Acid and Base

Water can act as both a Brønsted acid and a base. Between two water molecules, one can give
off a proton, leaving the hydroxide ion; and the other can accept this proton to become a hydronium
ion. This reaction is referred to as the self-ionization (or autoimization) of water. It occurs because of
the amphiprotic nature of water; that is, it can act as both a proton donor and an acceptor. The ions
exist in equilibrium with the water molecules.

The equilibrium constant of the reaction is called the ionization constant of water (Kw) which has
a constant value of 1.0 X 10^-14 M at 25 0C. The Kw allows for the calculation of either the
hydronium or hydroxide ion concentration when the other value is given. For example, if [H3O+]
is 6.2 X 10^-5 M then [OH-] is calculated simply as

In a neutral solution, the hydronium and hydroxide ion concentrations are equal, and can therefore
be calculated by taking the square root of Kw.

With [H3O+] [OH-] the equation is manipulated to get the concentrations of the ions.

When there is more [H3O+] than [OH-] the solution is described to be acidic. When [OH-] greater than
[H3O+], it is basic.
Sample Problems:
Compute the corresponding [OH-] or [H3O+] in each of the following conditions. Describe the
condition as acidic and basic.

MEASURING ACIDITY WITH pH

In 1909, Danish chemist SØren Peter Lauritz SØrensen introduced the pH scale as a way
of expressing the concentration of H+ in dilute solutions. pH, an abbreviation for power of
hydrogen, indicates the acidity or basicity of a solution. The "p" refers to the power or exponent of
the H concentration. The pH of a solution is mathematically defined as the logarithm of the
reciprocal of the H+ molar concentration.

At this point, take note that [H+] also refers to [H3O+], and that they have the same value.

Since a neutral solution has [H+] = 1.0×10^-7 , its pH can be calculated using the pH formula.

Acidic solutions have pH < 7 because [H+] is always greater than as implied by the negative logarithm.
Alkaline solutions have pH > 7 because [H+] is less than 1.0 X 10^-7. For alkaline solutions, it is more
convenient to use the term pOH, which is based on [OH-].

The relationship between pH and POH can be derived from the equilibrium expression of the
autoionization of water.

Therefore, the sum of pH and POH for a solution will always be equal to 14 because the product
of [H3O+] and [HO- is 1.0x10^-14.
 GENERALIZATION
Acids and bases have been used as laboratory chemicals for centuries, as well as in the home. Common
household acids include acetic acid (CH3COOH, vinegar), citric acid (H3C6H507, in citrus fruits), and phosphoric
acid (H3P04, a flavoring in carbonated beverages). Sodium hydroxide (NaOH, drain cleaner) and ammonia (NH3,
glass cleaner), are household bases. And acid-base chemistry occurs throughout the environment and organisms.
You may have noticed that some acids (e.g., acetic and citric) have a sour taste. In fact, the sourness was
a defining property in the 17th century: an acid was any substance that had a sour taste; reacted with active metals,
such as aluminum and zinc, to produce hydrogen gas; and turned certain organic compounds specific colors.
Similarly, a base (like the amines in fish) was any substance that had a bitter taste and turned the same organic
compounds different colors, Moreover, it was known that when an acid and a base react, each cancels the
properties of the other in a process called neutralization. Although these early definitions described distinctive
properties, they gave way to others based on molecular behavior.
We have the mathematical formula for equilibrium expression for the autoionization of water.

We have the mathematical formula in measuring for the acidity with pH.