L-129

For the most part, the responses occurring in the chemical sciences are breaking
and making of chemical bonds which is joined by some heat effects. Development
of chemical bonds discharges energy as heat and thus known as an exothermic
response. The response which is accompanied by absorption of heat is known as
endothermic response. Calorimetry is a scientific term managing the changes in
energy of the system by measuring the heat traded with its surroundings. A
calorimeter is a gadget intended to measure heat of response or physical changes
and heat capacity.
A calorimeter contains water or other substances with known heat capacity. The
heat, denoted as (Q) released by a reaction or process is absorbed by the
calorimeter and any substances in the calorimeter. If the only other substance in the
calorimeter is water, the following energy balance exists:

   = The heat flow for the calorimeter.

   = The heat flow for the water.

The individual heat flow rate can be directly related to the heat capacity and
temperature change for the substance. This can be denoted by the equation

 = The heat capacity of the calorimeter.

    = The heat capacity of the water.

Since the water and calorimeter are in thermal equilibrium they exhibit same
value.
The energy changes of a reaction that occur at constant pressure is termed as the
enthalpy change or the heat of reaction.
The heat capacity, which is defined as the amount of heat required to raise the
temperature of a given quantity of a substance by one degree Celsius, (unit is
J/ 0 C) of the entire system, denoted by C, is represented as the sum of the heat
capacities for the individual components involved in the reaction process.

 
Note: Since the calorimeter is insulated there is no heat exchange with the
surroundings. This can be shown as: Q reaction = -Q calorimeter
It is noted that the calorimeter exists as a fixed unit and thus its heat capacity is
also thought to be having a fixed value. Specific heat capacity is defined as the
heat required for raising unit mass of substance by one degree of temperature. It
has the units J/g0 C.
The relation between the heat capacity and specific heat of a substance is denoted
as C = ms.
m = mass of substance in grams.
C = Heat capacity.
s = specific heat.

L-30
Factors That Affect Rate
There are four main factors that can affect the reaction rate of a chemical reaction:
1. Reactant concentration. Increasing the concentration of one or more reactants
will usually increase the rate of reaction. This happens because a higher
concentration of a reactant will lead to more collisions of that reactant in a specific
time period.
2. Physical state of the reactants and surface area. The rate of reaction will be
limited by the surface area of the phases that are in contact if reactant molecules
exist in different phases, as in a heterogeneous mixture. For example, if a solid
metal reactant and liquid reactant are mixed, only the molecules present on the
surface of the metal are able to collide with the liquid molecules. Therefore,
increasing the surface area of the metal by turning it flat or chopping it into many
pieces will increase its reaction rate.
3. Temperature. An increase in temperature often increases the rate of reaction.
An increase in temperature will raise the average kinetic energy of the reactant
molecules. Therefore, a larger proportion of molecules will have the minimum
energy needed for an effective collision.
4. Presence of a catalyst. A catalyst is a substance that speeds up a reaction by
participating in it without being consumed. Catalysts give an alternate reaction
pathway to obtain products. They are important to many biochemical reactions.

L-31
Rate Laws
Typically, reaction rates decrease with time because reactant concentrations
decrease as reactants are converted to products. Reaction rates generally increase
when reactant concentrations are increased. This section examines mathematical
expressions called rate laws, which describe the relationships between reactant
rates and reactant concentrations. Rate laws are mathematical descriptions of
experimentally verifiable data.
Rate laws may be written from either of two different but related perspectives.
A differential rate law expresses the reaction rate in terms of changes in the
concentration of one or more reactants (Δ[R]) over a specific time interval (Δt). In
contrast, an integrated rate law describes the reaction rate in terms of the initial
concentration ([R]0) and the measured concentration of one or more reactants ([R])
after a given amount of time (t); integrated rate laws are discussed in more detail
later. The integrated rate law is derived by using calculus to integrate the
differential rate law. Whether using a differential rate law or integrated rate law,
always make sure that the rate law gives the proper units for the reaction rate,
usually moles per liter per second (M/s).
Reaction Orders
For a reaction with the general equation:
aA+bB→cC+dD
The experimentally determined rate law usually has the following form:
rate=k[A]m[B]n
The proportionality constant (k) is called the rate constant, and its value is
characteristic of the reaction and the reaction conditions. A given reaction has a
particular rate constant value under a given set of conditions, such as temperature,
pressure, and solvent; varying the temperature or the solvent usually changes the
value of the rate constant. The numerical value of k, however, does not change as
the reaction progresses under a given set of conditions.
The reaction rate thus depends on the rate constant for the given set of reaction
conditions and the concentration of A and B raised to the powers m and n,
respectively. The values of m and n are derived from experimental measurements
of the changes in reactant concentrations over time and indicate the reaction order,
the degree to which the reaction rate depends on the concentration of each
reactant; m and n need not be integers.

L-32
Zero-Order Reactions
Zero-order reactions (where order = 0) have a constant rate. The rate of a zero-
order reaction is constant and independent of the concentration of reactants. This
rate is independent of the concentration of the reactants. The rate law is:
rate = k, with k having the units of M/sec.
First-Order Reactions
A first-order reaction (where order = 1) has a rate proportional to the concentration
of one of the reactants. The rate of a first-order reaction is proportional to the
concentration of one reactant. A common example of a first-order reaction
is radioactive decay, the spontaneous process through which an unstable atomic
nucleus breaks into smaller, more stable fragments. The rate law is:
rate = k[A] (or B instead of A), with k having the units of sec-1
Second-Order Reactions
A second-order reaction (where order = 2) has a rate proportional to the
concentration of the square of a single reactant or the product of the concentration
of two reactants. The formula is:
rate = k[A]2 (or substitute B for A or k multiplied by the concentration of A times
the concentration of B), with the units of the rate constant M-1sec-1

References:
 https://vlab.amrita.edu/?sub=2&brch=190&sim=1546&cnt=1
 https://opentextbc.ca/introductorychemistry/chapter/factors-that-affect-the-
rate-of-reactions-2/
 https://chem.libretexts.org/Bookshelves/General_Chemistry/Map
%3A_General_Chemistry_(Petrucci_et_al.)/14%3A_Chemical_Kinetics/14.
03%3A_Effect_of_Concentration_on_Reaction_Rates%3A_The_Rate_Law
 https://www.thoughtco.com/chemical-reaction-orders-608182