PS403: PHYSICAL PHARMACEUTICS - II

B. Pharm. II Year II Sem

UNIT-I Drug stability:

i) Reaction kinetics: zero, pseudo-zero, first & second order, units of basic rate constants, determination of
reaction order.
ii) Physical and chemical factors influencing the chemical degradation of pharmaceutical product:
temperature, solvent, ionic strength, dielectric constant, specific & general acid base catalysis, Simple
numerical problems.
iii) Stabilization of medicinal agents against common reactions like hydrolysis & oxidation.
Accelerated stability testing in expiration dating of pharmaceutical dosage forms. Photolytic degradation
and its prevention
============================================================================

(i) Reaction Kinetics: Zero, Pseudo-zero, First & Second Order,

Units of Basic Rate Constants,Determination of Reaction Order

Reaction kinetics or Chemical kinetics is the study of the rate and mechanism of chemical changes that take
place during the chemical reaction.
Reaction kinetics or Chemical kinetics is the study of the rate and mechanism of chemical changes that take
place during the chemical reaction. In relation to the pharmaceutical formulation, it includes the study of
physical and chemical changes in drugs as well as the dosage form. The pace of a chemical reaction, the
stability test, and the half-life are all affected by a variety of circumstances.
The speed of a chemical reaction is defined by its velocity, while the order of the reaction is dictated by the
concentration of molecules that influence its rate. The rate of response is usually represented as,
Rate of reaction= -dA/dt
When the rate of reaction is stated in, the concentration of A falls with time while the concentration
of B grows as the reaction progresses.
Rate of reaction= -dB/dt
In an experiment with both A and B concentrations, it was revealed that the rate of response decreased with
time in the drug A concentration.
Molecularity of Reaction is a concept used to describe how the concentration of a reactant or reactants affects
the pace of a chemical reaction. The number of ions, atoms, or ions reacts in an elementary process to
produce the reactants. Among them, the molecular that undergoes chemical changes and yields the product,
the product is termed as unimolecular.
Drug Stability is the pharmaceutical dosage form that maintains the chemical and physical factors which
influence the chemical degradation of the product. Temperature, solvent, ionic strength, dielectric constant,
specific and general acid-base catalysis, and simple numerical issues are also determined by it. It also
stabilizes the drugs against hydrolysis and oxidation. Expiration date of pharmaceutical dosage forms using
accelerated stability testing, such as photolytic deterioration and its avoidance.

1
Zero Order Reaction
A constant rate process is used to describe a zero-order reaction. It is the reaction that is unaffected by the
concentration parameters of the reactants. In this situation, increasing the rate of the reactants will not
enhance the reaction rate. Other elements beyond concentration have a role in this response.
The rate of decomposition is expressed mathematically,
-dCx/dt = K------------------ (1)
Whereas, K is the specific rate constant for a zero-order.
Integrating the equation, X= Kt + constant ----------- (2)
A graph contains a plot of X. It results in a straight line equal to K. ‘K’ indicates the amount of drug degraded
per unit time. It intersects the line at time zero, which is equal to constant, in the graph. Concentration/time is
the unit of K.
Whereas, half-life = t ½ = Co/2k
Examples of zero-order kinetics are Vitamin A acetate to anhydrous Vitamin A and photolysis of cefotaxime

Pseudo-zero Order Reaction

It's the moment at which the chemical reaction starts. It cannot be physically observed. It is the phase that
occurs very instant of a reaction. Practically, the phase ‘chemical reaction’ of reactants begins at a very certain
time.
In a solid-state such as a tablet, the degradation of the drug is initiated by pseudo-zero order kinetics. It's the
response between the medicine and the amount of moisture in the dose form. Due to the presence of excess
solid drugs, it behaves like suspension. Mainly, the zero-order kinetic becomes the pseudo-order kinetics.

It intersects the line at time zero, which equals constant, in the graph. Concentration/time is the K unit. When
decomposition occurs, more amount of drugs releases from the suspended particles. That’s why the
concentration remains constant. Despite its deterioration over time, the most important point in suspension
stays constant. The drug equilibrium solubility in a given solvent at a given time is the suspension
concentration. The reservoir of the dispersed phase in suspension is responsible for the constant rate. The
suspended drug reservoir ensures constant concentration which is why it follows a zero-order reaction. In the
chemical reaction, the suspended particles convert to drug particles in solution. The order mostly shifts to a
first- order response.

First Order Reaction

It's a reaction whose rate is determined by the concentration of one of the reactants. For example, absorption,
distribution, elimination rates, and microbial death kinetics. As a result, the reaction rate is proportional to the
concentration of the reacting chemicals.
It can be expressed as:
Rate of the concentration decreases, -dCx/dt= KCx (3)
Where,

2
X= ‘a’, when t=0; t=x, the amount X at time t is (a-x)

Therefore,
-dCx/dt = K (a-x)
dCx/ (a-x) = -Kdt ---- (4)

Second-Order Reaction
It is the reaction in which the rate of reaction is dependent on the concentration of two reactants
raised to the power one. Therefore, A + B Product
Therefore, the equation

-dA/dt = -dB/dt = k2[A]1 [B]1 Where,

[A] = The concentration of A

[B] = The
concentration of B
k2 = rate constant
Units

Basic rate constants are measured in k. ‘k’ depending on the overall

orders of the reactions. In a zero-order reaction, the unit of k is M/s.

In a first-order reaction, the unit of k is 1/s.

In a second-order reaction, the unit of k is 1/(M-s).

Determination of Reaction Order

The order of the reaction defines the relationship of the rate and concentration of the chemical reaction. In the
case of determining the order of the reaction, there are several methods to follow:

Substitution Method In a reaction of two molecules, the products show incompatible results in some cases.
It will, however, be replaced with a different chemical molecule. It shows better results and effects in
reaction results. In general, this strategy enhances the reaction's efficacy and outcomes.

Initial Rate Method

In the graph, the points are plotted against concentration. The gradient at time = 0 also defines the starting
rate. In the graph, if the plot draws a straight line that signifies a first-order reaction. If the reaction is
independent of the concentration, it is termed a zero-order reaction. If a curve appears in the graph at some
point, it signals a second order reaction.

3
Data Plotting Method
If the plotting is linear such as concentration against time, it
is a zero-order reaction. If the plotting is linear such as c
against time, it is a first-order reaction.
If the plotting is linear such as 1/c against time, it is a second-order reaction.

Half-Life Determination Method

It defines the relationship between the half-life of a reaction and the
concentration of all reactant's id similar. Whereas, n = order of the reaction.
t1/2 is directly proportional to 1/an-1
If the two reactions are occurring at different initial concentration,
the half-lives of a1 and a2 is, n = log (t1/2(1))/(t1/2(2))/ log (a2/a1) + 1
The process of chemical kinetics in relation to pharmaceutical ingredients determines the degradation of the
drug according to the concentration
against time. The degradation starts after exposing the drug to air and absorbing moisture. Chemical
kinetics, on the other hand, explains the chemical changes that occur in a medicine based on the reaction
order.
(ii) Physical and Chemical Factors Influencing the Chemical Degradation of Pharmaceutical
Product:Temperature, Solvent, Ionic Strength, Dielectric Constant, Specific & General acid base catalysis

Pharmaceutical products are medicines prepared for human use and are called pharmaceutical
products. These are chemically prepared with specific formulation and controlled by pharmaceutical
legislation (authorized). Different brands or pharmaceutical companies prepare them in different
packaging. On the other hand, chemical degradation is the process that breaks a chemical molecule into small
chemicals. It is also called chemical decomposition or thermal decomposition. This affects the
pharmaceutical value of the drug.
Some external factors can influence the degradation of a pharmaceutical product. These factors are
physical and chemical in nature, the specific influences are discussed critically. This can show a precise
pharmaceutical application and degradation procedure.
Influence of the External Factors
External factors present the environmental reasons that show effects on the particular system of
pharmaceutical product. These factors are,
 Temperature
 Solvent
 Ionic Strength
 Dielectric Constant

4
  Acid-Base Catalyst

Temperature
When a specific amount of temperature is applied to a pharmaceutical product, then it starts to activate the
molecules inside. According to the collision theory, the high temperature starts the collision between the
chemical molecules of the product. Overall, it increases the chemical degradation of a pharmaceutical
product. On average, every reaction becomes two to three minutes faster with every 10-degree increase in
temperature. With the increase in temperature, the chemical composition of a compound breaks down to
its molecular level. This decreases the ability of the compound and increases the rate of degradation of the
compound.
This is one of the reasons that pharmaceutical products or medicines are suggested to keep in cold places. It
is most preferable to have cold storage in the pharmaceutical industry. In this way, the medicines become
safe and best applied.

Solvent
A solvent is defined as any chemical compound that is capable of dissolving any other substance without
changing the chemical nature of the substance or the solvent itself. Solvents are classified into two types.
Aqueous solvent or inorganic solvent, which includes water, and non-aqueous or organic solvent, which
includes alcohol, glycerine, and polyethylene glycol. Solvent has a significant influence on the rate of
degradation of a drug. The effect of the dielectric constant and viscosity of a solvent can alter the rate and
mechanism of a chemical reaction. The effect of the dielectric constant on the degradation of a chemical
compound is already under resource with different chemicals, which include aspirin, phenoxybenzamine,
triprolidine, and levofloxacin. Besides, it is also recorded that the rate constant and viscosity of a solvent
has a linear relation to the degradation of the chemical substance. The selection of a particular solvent and
cosolvent is essential for the stability and degradation of any pharmaceutical formulation. Different factors
must be considered before selecting a solvent. These factors include the chemical nature of the substance, the
polar character of the substance, and the behavior of the drug on a particular medium. The solubility of a
compound is calculated in values of kobs. The kobs value for water is recorded as 78.5, and the kobs value of
ethylene acetate is recorded as 6.0. The value of kobs depends on the viscosity and dielectric constant of the
compound.

Ionic Strength
A charged ion holds an inactive strength state. This is transferable and applied in a different reaction. It
influences the chemical degradation of a pharmaceutical product. For example, if two reactants are A and B.
Their charges are z1 and z2. Then the internal chemical equation will look like,
Az1 + Bz2 = [A……B](z1+z2)
Overall, the ionic strength will show its effect between the charges. This can also influence the chemical

5
degradation level in a pharmaceutical product. On the other hand, this can be calculated for further precaution
and essential storage procedures. Eventually, it helps to build a proper supply chain of safe and secure
medicine. This strength differs with the product and formulation intensity of the medicine. This will be
documented in

different phases, such as laboratory trials of medicine.

Dielectric Constant
Every electric field holds some energy in it for further transfer or transformation. The measuring unit of this
stored energy is the dielectric constant. This is calculated through a ratio of permeability of the material to
the electric permeability of free space. This shows an essential strength factor in an electric field. This effect
can be calculated through,
In k = In kE=.infinity. – NzAzBe2 / RTr|E
This equation can help to calculate the intensity or effect of the Dielectric constant in the chemical
degradation of pharmaceutical products. It also depends on some chemical factors that are associated with the
overall degradation reaction.
This image shows the connection between Dioxane, Dielectric constant, and Rate Constant. This presents the
overall effectiveness of the procedure. On the other hand, it helps in the practical calculation of the present
materials. Overall, this section presents the quantitative analysis of the dielectric constant in the chemical
degradation of the pharmaceutical product.

Acid-Base Catalyst
A catalyst is a chemical molecule or substance that increases the speed of the reaction but remains unchanged
till the end. In that case, it does not affect the overall temperature change in the reaction, delta G.
This calculation can show the quantitative measurement of the overall temperature change into the reaction
that remains zero in terms of catalyst effect.
Acid-base catalyst is one of the categories that present the presence of an acid or base. That molecule will
improve the overall speed of the reaction. In this way, the acid-base catalyst will be effective in overall
chemical degradation.

The time of degradation of any pharmaceutical product is mentioned on the packing of the product. Different
physical and chemical factors are noted and calculated for determining the rate of degradation of a chemical
substance. The pharmaceutical companies have introduced special departments for ensuring, calculating, and
determining the rate of degradation of a chemical compound. In the article, we were introduced to such
factors that help in the easy determination of the rate of degradation of a chemical compound. These factors
include acid-base catalyst, temperature, solvent, dielectric constant, and ionic strength.

6
(iii) Stabilization of Medicinal Agents against Common Reactions like Hydrolysis & Oxidation
Mainly, drug substances are the chemical entities that intend to go through chemical changes or degradation.
Mainly, drug substances are the chemical entities that intend to go through chemical changes or degradation.
Molecular changes and the presence of different functional groups cause it. Degradation starts due to several
factors such as temperature, moisture, pressure, etc. A degradation reaction can also occur in organic and
aqueous solvents. The drug substances undergo various pathways that cause the degradation of the product.
Various reactions promote drug degradation of pharmaceutical products. Among them, Hydrolysis and
Oxidation are the two reactions that undergo further drug degradation.

A) Hydrolysis:
Hydrolysis involves the reaction of the chemical compounds with water that produces two or more
products. The bond on the chemical compound is formed by the addition of water. In an aqueous solution and
liquid dosage form, the hydrolytic reaction is the most common factor. A substance that contains ester,
amides, imides, carbamates, lactones, nitriles, and carbohydrate groups will be destabilized by this substance.
In this case, the pH of the medium plays an essential role. There are also varieties of drugs susceptible to acid
as well as alkaline hydrolysis.
The drugs that change by hydrolysis are aspirin, paracetamol, sulfacetamide, indomethacin, procaine,
digoxin, riboflavin, benzodiazepines, penicillins, lincomycin, chloramphenicol, and cephalosporins.

(i) Hydrolysis of Ester [R-COO-R’]

Water or OH- ions attack the ester group nucleophilically during the hydrolysis of ester. It undergoes a
second-order reaction and is one of the most important reactions of hydrolysis.
On acidic hydrolysis of ester, it yields carboxylic acid and alcohol whereas
basic hydrolysis of ester, it yields carboxylate salt and alcohol.
For example: Aspirin or Acetylsalicylic acid, and procaine.
In the hydrolysis of Aspirin, it produces salicylic acid and acetic acid. On the other hand, this reaction is
completely accelerated by temperature.
Hydrolysis of Procaine is primarily controlled by this reaction. In this chemical reaction, it forms 4-
aminobenzoic acid and dimethyl amino ethanol. Ionization of the molecule influences the reaction here.

(ii) Hydrolysis of amides [R-C(=O)-NR’R”]

It contains compounds that have amide bonds. In comparison to ester bonds, amide bonds are less
susceptible to hydrolysis. Since this bond is electrophilic, the carbonyl carbon of the amide has a lower
electrophilicity. In the reaction, the carbon-nitrogen bond breaks down and yields COOH, NH3, or amine.
For example, Paracetamol, and Sulfacetamide.

7
 The hydrolysis of Paracetamol leads to the formation of 4-aminophenol and acetic acid.
Sulfacetamide hydrolyzes to produce acetic acid and sulphanilamide.
Sulfanilamide undergoes oxidation to yield 4,4’- azobenzenedisulfonamide. On further oxidization, it yields
4,4’-azoxybenzenedisulfonamide on exposure to light. This reaction shows the formation of the reddish-
brown color from yellow color.

(iii) Hydrolysis by Ring Opening

The hydrolysis of the drug molecules occurs by the cleavage of C-N bond.
a) Riboflavin [C₁₇H₂₀N₄O₆]
Riboflavin is a water-soluble compound popularly marketed as vitamin B2.
Riboflavin is hydrolyzed in a basic medium converting it into two compounds.

The dextrorotatory part 1,2-dihydro-6,7-dimethyl-2-keto-I-D-ribityl-quinoxaline-3-carboxylic acid and

levorotatory part with the IUPAC name 6,7-dimethyl-4-D-ribityl-2,3-dioxo-1,2,3,4-tetrahydro quinoxaline.
The reduction of riboflavin absorption at 445 nm is accompanied by the degradation reaction, which is
enhanced by increasing the temperature.

b) Norfloxacin
Norfloxacin is a fluoroquinolone antibiotic derivative used for solving digestive system-related problems.
Norfloxacin undergoes hydrolysis and breaks the piperazine ring cleavage in an alkaline medium forming
diethylene norfloxacin.
Desethylene norfloxacin under the presence of light father hydrolyzes and is converted to N-acetyinorfloxacin.

B) Oxidation
Oxidation is the process by which an element or compound gains oxygen or loses an electron from its
outermost shell. An oxidizing agent or oxygen initiates the oxidation process. It has been noted that drugs are
easily oxidized in contamination with air while manufacturing, packing, and storage. The pH of the medium
is capable to affect the rate of oxidation which results in ionization and change in the redox potential of the
compound. Many compounds undergo the process of oxidation. These compounds include ascorbic acid,
morphine, phenols, etc.

(i) Oxidation of Ascorbic acid

Ascorbic acid popularly marketed as vitamin C is a highly complex organic molecule that is soluble in water.
The ascorbic acid molecule undergoes oxidation, changing its chemical structure and property. Ascorbic acid
can be converted to dehydroascorbic acid during this oxidation step.
H2A DHA+ 2e- + 2H+
Di-hydro-ascorbic acid is converted to di-keto-gulonic acid in an alkaline solution with the involvement of the
process of hydrolysis.

8
(ii) Oxidation of morphine
Morphine is a natural tranquilizer obtained from the plant opium. It is wildly used as a painkiller after any
major surgery. Morphine is oxidized in an aqueous solution by air and light. After oxidation morphine is
converted into two different compounds. Morphine is oxidized to Pseudomorphine and Morphine-N-Oxide in
an aqueous solution.
The dextrorotatory form of oxidized morphine is popularly marketed as noxydimorphine or pseudomorphine.

The levorotatory form of oxidized morphine is popularly marketed as morphine-N-oxide.

(iii) Oxidation of phenols
Phenol is a white, crystalline solid, aromatic, water-soluble, and volatile compound used for both household
purposes and in the pharmaceutical industry for synthesis purposes. Phenol has a resonating structure. The
hydroxyl group of the phenol moiety is capable of donating an electron and initiating the process of
oxidation. A radical is formed as a result of the proton being removed from the atom. Phenol deprotonation
occurs at higher pH levels. The phenolate anion catalyzes the auto-oxidation process in a considerable way.
The phenolate anion is a powerful nucleophile that can react with electrophilic species on both ends of the
electron chain.
Due to the absence of hydrogen ions on the hydroxyl bearing carbon, Phenols can be easily oxidized. Para-
benzoquinone is the dicarbonyl compound that results from the chromic acid reaction.
Hydrolysis and oxidation reaction also causes the degradation of pharmaceutical products. Not only that but
several reactions can cause the degradation of drugs. The reactions such Decarboxylation, Elimination,
Isomerisation, Dimerization, Epimerization, Dehydration, Dehydrogenation, and Dehalogenation.

Accelerated Stability Testing in Expiration Dating of Pharmaceutical Dosage Forms

When pharmaceuticals are subjected to expedited stability testing, the medications produced in the factories
are found to be stable in shelf life.
When pharmaceuticals are subjected to expedited stability testing, the medications produced in the factories
are found to be stable in terms of shelf life. At a certain period, the drug particles begin to degrade and lose
their stability. For this reason, the finished pharmaceutical drugs must contain an expiration date on the drug
product. In the finished pharmaceutical product, test stability is also an essential point to follow. It measures
the appropriateness and accuracy of the expiration date of the drug.
Every drug particle is different as it shows a huge difference in the physio-chemical properties of the
excipients, drug manufacturing process, drug formulation, containers and closures, proposed storage
conditions, and the drug stability to maintain the quality as well as purity. The quality and stability of
pharmaceutical products are increased by preservatives and antioxidants. Due to the differences in drug
particles, it is impossible to apply a certain set of rules for each product in all situations. For the finished
product, Current Good Manufacturing Practice (cGMP) has brought requirements concerning the expiration
date of the manufactured products

9
Expiration Dating
Absence of an Expiration Date
The lack of an expiry date on items manufactured after September 29, 1979 is intended to trigger regulatory
action. It does not apply to the medications listed in 211.137 (e), (f), and (g).

Exemptions
As per the exemption of 211.137, Over-the-counter (OTC) is utilized in acceleration testing practice. These
are the drugs that remain stable for 3 years. According to the study, over-the-counter medications like
paracetamol are safe, but excessive usage can lead to Hepatic Necrosis.

Products Intended for Reconstitution

The drugs are meant for reconstitution or do not have expiration data for the reconstituted product. After that,
another expiration date will be renewed for the particular product after reconstitution. The fact is termed as
out of compliance with 211.137 (c). There are also few studies on the expiration date of drugs.

Stability Testing
Stability tests provide evidence of the degree to which the performance of a substance or product fluctuates
over a certain time and in the context of environmental conditions, such the temperature, humidity, and light.
The research investigations look at characteristics that can vary over time and have an impact on the product's
quality, safety, and efficacy.
Testing typically covers the microbiological, chemical,

and physical aspects: Physical Surface:

Appearance, melting point, and water content.

Chemical Assay and degradation products, associated chemicals and solvents that remain
Microorganisms: Growth in microorganisms as well as the efficiency of preservatives, like
Antimicrobials, antioxidants as well as antimicrobials.

The frequency of testing points for long-term studies must be enough to determine the stability profile of
extended duration.
For drugs with the potential for re-testing that is at least 12 months the testing frequency in a long-term
storage environment is typically every three months for the first year, every six months during the second
year, and then annually throughout the time of the proposed re-test.
The recommended testing interval for the intermediate storage is at least four times, which includes the final
and initial time points, in an entire 12- month study.
For storage conditions with accelerated speed, the test frequency should be set to be at least three times,
which includes the first and last times for a 6-month study. A substance that is a drug must be tested under
conditions of storage that test its thermal stability as well as its susceptibility to humidity.

10
Written Stability Testing Program
The stability test of a pharmaceutical product is mainly done for storage condition and expiration date.
For the stability testing of Active
Pharmaceutical ingredients (API), drugs in processing, as well as marketed pharmaceutical products WHO
and ICH have introduced several guidelines. The main aim of the stability test is to undergo a re-test. Not
only that, it defines storage conditions as well that could influence the quality of the pharmaceutical product.
Furthermore, it is influenced by elements such as temperature, humidity, and light. That’s why it is required
to undergo a written stability testing program.

Supportive Stability Data

Number and Size of Batches
Accelerated testing is done in smaller batches than normal production. For the long-term ability program,
three initial batches are minimal to establish an expiration date. Stability testing of the drudrugsis not only
limited to certain production batches. In this instance, a percentage of each year's manufacturing batches is
subjected to a continuous stability programme. The complex unit is dosage form. In the production process,
there are certain continued variables such as suppliers, raw materials, and equipment.

Accelerated Studies
Accelerated life testing ipracticeactise of submitting a product to conditions (stress, strain, temperatures,
voltage, vibration rate, pressure, and so on) that are outside of its usual service parameter to find flaws and
potential modes of failure in a short amount of time.
Engineers can forecast a product's service life and maintenance intervals by examining the product's response
to such testing.

Test Intervals
The interval test is one variation of the gap test. The main concept is to look at the time intervals
between occurrences of the same value. Consider the case where random returns the value 3.
Up to and including the next occurrence of 3, count the number of
values generated by random. Rep this process for each time the value
3 appears in the output sequence.
Count the number of 1, 2, 3, and so on length separations.

Calculate a chi-square statistic for each separation length using these counts and the expected counts, and
compare the result to the critical value of a chi-square random variable with the proper number of degrees of
freedom and a probability of 0.95.
When a tentative expiration dating term of more than three years is established purely based on accelerated
testing data, it is discouraged. In the article, we are introduced to different types of tests that are used to
determine the stability of a pharmaceutical product.

11
 Photolytic Degradation and Its Prevention
Photolytic Degradation is defined as any change or alteration on the main chemical constituent of a
drug, food, paints, dyes, inks, pesticides, etc., due to light or Photon particles.

The term photolytic Degradation is coined due to the action of Sunlight and air on a product, causing
both oxidation and hydrolysis. The different factors causing photolytic Degradation and the various
consequences of photolytic degradation will be recognized and also explains the mechanism of photolytic
Degradation. Besides, you will know the different methods by which you can protect a chemical from being
degraded due to light and photon particles.

Factors Causing Photolytic Degradation

There are certain factors that are responsible for photolytic Degradation. These factors are essential to
determine the degradation rate due to light.
This factor includes:
1. Introduced of Carbonyl group into the chemical constituent of the compound.

2. Introductionof any unsaturated Bond in the chemical constituent of the compound.

3. Use of any catalytic Residue is capable enough to affect the photolytic Degradation
4. Use of solvent catalyst or any additives can easily affect the chemical constituent and photolytic degradation
of a compound
5. Introduction of traces of metal such as iron, Nickel or chromium and their oxide can affect the chemical
constituent and photolytic degradation of a moiety
6. Use of hydroperoxide prevents the compound from getting degraded from light or Photon particles.

7. Light and Photon particles have a tough time degrading compounds gathered from a dirty or smoggy
environment.
Effect of photolytic Degradation
Photolytic degradation effects both the physical and chemical properties of a compound.

The physical changes can be distinguished with naked eyes.

The chemical changes are determined by specific tests and observations.

The main effects that are observed (physical changes) in a photolytic degradation include:
1. Photolytic degradation effect the color of a chemical moiety.

2. It is capable of effecting the solubility of a compound

3. It can effect the Pka value of the compound

4. It is capable of effecting the order of the compound
5. It can change the viscosity and dissociation constant of a compound

Prevention from photolytic Degradation

Food must be protected from photolytic degradation at all times.
When some nutrients, for example, are exposed to sunshine, they degrade.
In the case of beer, UV light induces the breakdown of bitter hop chemicals to 3-methyl-2-butene-1-thiol,
resulting in a change in flavour.

12
Beer bottles are frequently composed of amber-coloured glass, which has the potential to absorb UV light
and so avoid this process. Organic paints, inks, and dyes are more photodegradable than inorganic paints,
inks, and dyes. Ceramics are nearly commonly coloured with non-organic origin materials in order for the
material to withstand photolytic degradation and retain its colour even under the harshest conditions. Because
of the scope of agriculture and the extensive usage of chemicals, the photolytic degradation of pesticides is of
major interest.
Pesticides, on the other hand, are chosen in part because they do not photolytic degrade rapidly in the
sunshine, allowing them to perform their biocidal function.
To improve pesticide decomposition, additional modalities (e.g., photosensitizers, photocatalysts, and
hydroxyl radical-forging reagents) such as hydrogen peroxide are used to form toxic hydroxyl radicals that
attack the pesticides.
Pharmaceutical photolytic degradation is of importance since pharmaceuticals are prevalent in many water
systems.
Toxicity, endocrine disruption, and genetic damage are all negative consequences on aquatic organisms.
Photolytic degradation of pharmaceuticals must also be avoided in the primary packing material.
Pharmaceuticals are widely protected against UV radiation in this case by amber glasses such as Fiolax amber
and Corning 51-L.

A small amount of UV light can pass through the packaging of colloidal silver and iodine (in the form of
Lugol's solution) and prevent them from deteriorating.
A common synthetic polymer that can be attacked is polypropylene, in which the tertiary carbon bonds in its
chain topology serve as targets.
UV rays combine with these bonds to produce free radicals, which then react with oxygen in the atmosphere
to form carbonyl groups in the main chain.
In extreme conditions, surfaces of exposed products may discolour and crack, and the product may disintegrate
completely.
Fiber products such as rope used outdoors will have a short product life since abrasion attacks the outer
fibers first and they will degrade rapidly. It is possible to notice a discoloration of the rope as well,
indicating an early problem.
UV degradation may also be a problem for polymers with UV-absorbing groups, such as aromatic rings.
Aramid fibres, such as Kevlar, are very UV-sensitive and must be protected from the sun's harmful effects.
The modification of materials caused by light is known as photolytic Degradation. The phrase is commonly
applied loosely to the combined action of sunshine and air, which results in oxidation and hydrolysis. In the
article, we are introduced to different factors that are responsible for photolytic Degradation. Moreover, we
are introduced to the different effects of photolytic Degradation. The article also acknowledges the different
preventive measures that will protect a chemical from photolytic degradation.

13