CHEMISTRY II

ANALYTICAL CHEMISTRY
Q1) Answer the following (Any Five)

a) Define Analytical Chemistry.

Ans
The branch of chemistry which deals with the study of the separation, identification, qualitative
and quantitative determination of the compositions of different substances, is called analytical
chemistry.
b) Define the term Molarity.
Ans
Molarity (M) is defined as the number of moles of the solute dissolved in one Litre of the
solution.
It is expressed as:
Molarity (M) =........Moles of solute………
Volume of Solution in Litre

c) List the different types of organic compounds.

Ans 1 ) Acyclic or Open Chain Compounds: 2 )Alicyclic or Closed Chain or Ring Compounds:
3) a) Benzenoid aromatic compounds 4) Non-benzenoid aromatic compounds

1 2 3 4
d) Define the term R.
Ans The Rf (retardation factor) value is the ratio of the solute’s distance travelled to the
solvent’s distance travelled.

e) State the equation for operational definition of ph.

Ans pH, p H = - log [ H ] + It is simply the calculation of the negative log of the concentration of
Hydrogen ions. The pH of any solution depends on the concentration of Hydrogen ions. pH is a
temperature-independent quantity.

f) Which solvents are used as mobile phase for supercritical-fluid Chromatography?

Ans Supercritical fluid chromatography (SFC) is a form of normal phase chromatography that
uses a supercritical fluid such as carbon dioxide as the mobile phase.
02) a) Answer the following:

i) How will you separate Phenol-Neutral Mixtures? Give chemical reactions involved in it.
Ans To separate phenol-neutral mixtures, you can use liquid-liquid extraction, where the phenol
is extracted into a solvent while the neutral compound remains in the aqueous phase. Here's a
general method:
1. Dissolve the phenol-neutral mixture in a water-immiscible organic solvent like
dichloromethane or ethyl acetate. The phenol will partition into the organic phase, while the
neutral compound will remain in the aqueous phase.
2. Separate the organic and aqueous layers.
3. Repeat the extraction process if needed to ensure complete separation.
4. Recover the phenol from the organic phase by evaporating the solvent.
Chemical reaction involved in the extraction process is:

The neutral compound remains unaffected by this reaction and stays in the aqueous phase.

ii) An organic compound contains 34.80% oxygen, 52.20% carbon and 13.00% Hydrogen.
Calculate empirical formula and molecular formula for the compound.
[Given: Molecular Weight = 92 g/mole, Molar Mass of C = 12, H = 1 and O = 16 g/mole].
Ans
b) Answer the following
i) Give applications of ph meter
Ans pH meter is an instrument used to measure acidity or alkalinity of a solution - also know as
pH. pH is the unit of measure that describes the degree of acidity or alkalinity. It is measured on
a scale of 0 to 14.

ii) Give the classification of chromatography on the basis of physical state of phase.
Ans Mobile phase flowing over the stationary phase is a gaseous or liquid phase. If mobile
phase is liquid it is termed as liquid chromatography (LC), and if it is gas then it is called gas
chromatography (GC). Gas chromatography is applied for gases, and mixtures of volatile
liquids, and solid material.

Q3) a) Answer the following

i) Give the applications of paper chromatography
Ans Paper chromatography is a simple and widely used technique with various applications,
1. **Separation of Amino Acids:** Paper chromatography is commonly used to separate and
identify amino acids in biological samples.
2. **Separation of Dyes:** It is used in the textile industry to separate and analyze dyes used in
fabrics.
3. **Forensic Analysis:** Paper chromatography is used in forensic labs to separate and identify
components of ink and other substances found at crime scenes.
4. **Environmental Analysis:** It is used to analyze pollutants and other compounds in
environmental samples such as water and soil.
5. **Biochemical Analysis:** Paper chromatography is used in biochemistry to separate and
identify various biomolecules such as amino acids, sugars, and lipids.

ii) Calculate p-functions for each ion in following solutions

1) 0.045 M NaBr
Given that the concentration of NaBr is 0.045 M, the concentration of each ion is equal to the
initial concentration of the salt since it dissociates completely.
Therefore, for NaBr:
- [Na+] = 0.045 M
- [Br-] = 0.045 M
To calculate the p-functions, we use the formula:

So, the p-functions for Na+ and Br- ions in a 0.045 M NaBr solution are approximately 1.35.
2) 0.0250 M in MgBr2
Ans
Given that the concentration of MgBr2 is 0.0250 M, the concentration of Mg2+ ions is equal to
the initial concentration of MgBr2, and the concentration of Br- ions is twice the initial
concentration of MgBr2 since each MgBr2 molecule produces two Br- ions upon dissociation.
Therefore, for MgBr2:
- [Mg2+] = 0.0250 M
- [Br-] = 2 * 0.0250 M = 0.0500 M
To calculate the p-functions, we use the formula:

So, the p-functions for Mg2+ and Br- ions in a 0.0250 M MgBr2 solution are approximately 1.60
and 1.30, respectively.
B) Answer the following
i) How will you detect presence of phosphorous element in an organic compound by
Lassigne's test?
Ans
Lassaigne's test is used to detect the presence of nitrogen, sulfur, or halogens, but not
phosphorus, in an organic compound. If you want to detect the presence of phosphorus in an
organic compound, you can use the following method:
1. **The Lucas Test:** The Lucas test is used to detect the presence of phosphorus in an
organic compound. It involves the following steps:
- Add a small amount of the organic compound to a test tube.
- Add a few drops of Lucas reagent (a mixture of concentrated hydrochloric acid and
anhydrous zinc chloride) to the test tube.
- Heat the mixture gently.
- If a white precipitate is formed, it indicates the presence of phosphorus in the organic
compound.
This test is based on the formation of a white precipitate of phosphorus(V) chloride (PCl5) when
phosphorus is present in the organic compound.
ii) Give the applications of gas chromatography
Ans Gas chromatography (GC) is a versatile analytical technique with numerous applications
across various industries. Some key applications include:
1. **Chemical Analysis:** GC is used to separate, identify, and quantify components in
complex mixtures. It is widely used in pharmaceuticals, food and beverage, environmental
analysis, and forensic science.
2. **Environmental Monitoring:** GC is used to analyze air, water, and soil samples for
pollutants and contaminants, such as volatile organic compounds (VOCs) and pesticides.
3. **Food and Beverage Industry:** GC is used to analyze food products for additives, flavors,
pesticides, and other contaminants. It is also used in beverage analysis, such as the analysis of
alcoholic beverages.
4. **Petrochemical Industry:** GC is used to analyze petroleum products, such as fuels and
lubricants, for composition and quality control purposes.
5. **Drug Analysis:** GC is used in forensic and clinical laboratories to analyze drugs and their
metabolites in biological samples, such as blood and urine.
6. **Research and Development:** GC is used in research laboratories for studying chemical
reactions, developing new analytical methods, and identifying unknown compounds.

4) a) Answer the following

i) Describe the construction of a Calomel electrode.
Ans The calomel electrode consists of a glass tube containing a saturated potassium chloride
(KCl) solution and a silver-silver chloride (Ag-AgCl) electrode immersed in the solution. The
Ag-AgCl electrode is connected to the external circuit for measurement, while the KCl solution
provides a stable ionic environment. The electrode is housed in a glass tube sealed at one end,
with the open end serving as the reference junction. This construction ensures a stable
reference potential for accurate electrochemical measurements.
ii) Distinguish between mass and weight
Ans In analytical chemistry, the distinction between mass and weight is crucial, especially when
measuring substances and determining their properties. Here's how they differ in analytical
chemistry:
1. **Mass:**
- Mass refers to the amount of matter in a substance and is usually measured in grams (g) or
kilograms (kg).
- In analytical chemistry, mass is determined using a balance, which compares the unknown
mass to a known mass.
- Mass is an intrinsic property of a substance and is independent of its location. It remains the
same regardless of the gravitational field.
2. **Weight:**
- Weight is the force exerted on a substance due to gravity and is measured in newtons (N) or
other force units.
- In analytical chemistry, weight is not typically used to measure substances because it can
vary depending on the gravitational field strength.
- Weight is dependent on the gravitational field and varies with location. For example, an
object will weigh less on the moon than on Earth due to the moon's weaker gravity.
b) Answer the following:
i) Discuss the common analytical problems
Ans.
Analytical chemistry, as a field, encounters various challenges in ensuring accurate and precise
measurements. Some common analytical problems include:

1. **Sample Contamination**: Contamination from environmental sources or improper

handling can lead to inaccurate results. Proper sample preparation and handling techniques are
crucial to minimize this issue.
2. **Matrix Effects**: The sample matrix can interfere with the analytical measurement,
affecting the accuracy and precision of the results. Techniques such as sample dilution or
extraction are often used to mitigate matrix effects.
3. **Calibration Errors**: Improper calibration of instruments can lead to inaccurate
measurements. Regular calibration with appropriate standards is necessary to ensure reliable
results.
4. **Instrumental Drift**: Over time, instruments can drift, leading to variations in
measurements. Regular maintenance and recalibration can help mitigate this issue.
5. **Sensitivity**: Some analytes may be present in very low concentrations, requiring sensitive
detection methods. Ensuring the sensitivity of the analytical method is essential for accurate
measurements.
8. **Data Analysis**: Proper data analysis is essential to extract meaningful information from
analytical measurements. Incorrect analysis can lead to misinterpretation of results.

ii) How is Tollen's reagent prepared? Where is it used?

Ans
Tollens' reagent, Sodium hydroxide, is added to a solution of silver nitrate dropwise until a light
brown precipitate is obtained. To this, concentrated ammonia solution is added dropwise until
the brown precipitate of Ag2O dissolves completely. The amount of ammonia should be
sufficient enough to dissolve the precipitate completely until a clear solution is obtained. The
complex obtained at the end is (Ag(NH3)2)+ in which silver is in +1 oxidation state, i.e. Ag+ acts
as the main component of the Tollens' reagent. NaOH that was initially used is reformed at the
end and helps in maintaining the needed pH balance.
Q5) Answer the following (Any Two):
i) What is TLC? What are various types of TLC? Give advantages of TLC.
Ans Types of TLC include:
1. **Normal Phase TLC:** In this type, the stationary phase is polar (e.g., silica gel) and the
mobile phase is nonpolar. Compounds are separated based on their polarity, with more polar
compounds interacting more strongly with the stationary phase and moving more slowly.
2. **Reverse Phase TLC:** Here, the stationary phase is nonpolar (e.g., C18-bonded silica)
and the mobile phase is polar. This type of TLC is useful for separating nonpolar compounds.
3. **Chiral TLC:** This type of TLC uses a chiral stationary phase, allowing for the separation of
enantiomers (optical isomers).
4. **Planar Chromatography:** TLC is a type of planar chromatography, where the stationary
phase is a thin layer spread over a flat surface.
Advantages of TLC include:
- **Rapid Analysis:** TLC is a relatively quick technique, with separations typically taking
minutes to hours.
- **Low Cost:** TLC plates and solvents are relatively inexpensive, making it a cost-effective
technique.
- **Simple Procedure:** TLC does not require specialized equipment and can be performed with
basic laboratory tools.
- **High Sensitivity:** TLC can detect compounds at low concentrations, making it useful for
trace analysis.

ii) Calculate the number of moles and millimoles of salicylic acid that are contain in 5.00
g of the pure salicylic acid.
[Given: Molar Mass of Salicylic acid = 138 g/mole]
Ans
B) Indicate how many significant figures are each of the following numbers.
1) 0.045050.
1) The number 0.045050 has six significant figures.
- The zeros between the nonzero digits 4 and 5 are significant because they are between
significant figures.
- The zero to the left of the decimal point is not significant as it only serves to locate the
decimal point.
- The zero to the right of the decimal point and after the last nonzero digit 5 is significant as it
indicates precision.
2) 1.2638 x 106
2) The number 1.2638 x 10^6 has five significant figures.
- The digits 1, 2, 6, 3, and 8 are all significant. - The exponent 6 does not affect the number
of significant figures; it only indicates the magnitude of the number.

C) Explain paper chromatography with reference to -

i) Stationary and Mobile phase.
Ans
In chromatography, the stationary phase and the mobile phase are two key components that
help separate the components of a mixture based on their different interactions with these
phases.
1. **Stationary Phase:** This phase does not move during the chromatographic process. It is
typically a solid or a liquid supported on a solid. The molecules of the stationary phase interact
with the components of the mixture differently, causing them to separate based on their affinity
for the stationary phase. Examples of stationary phases include the solid support in column
chromatography or the coated surface in thin-layer chromatography (TLC).
2. **Mobile Phase:** This phase moves through or over the stationary phase, carrying the
mixture along with it. The mobile phase is typically a gas or a liquid. As it moves, the
components of the mixture distribute themselves between the stationary and mobile phases
based on their chemical properties, leading to separation. In gas chromatography (GC), the
mobile phase is a carrier gas, while in liquid chromatography (LC), it is a liquid solvent.
ii) Development of Chromatogram.
Ans
Sure, here's a brief overview of the development of a chromatogram:

1. **Sample Application:** The sample is applied to the stationary phase. This can be done by
spotting a small volume of the sample onto a TLC plate or injecting it into a chromatography
column.
2. **Mobile Phase Movement:** The mobile phase (gas or liquid) moves through or over the
stationary phase, carrying the sample components along with it.
3. **Separation:** As the mobile phase moves, the components of the sample distribute
themselves between the stationary and mobile phases based on their affinity for each phase.
This differential movement leads to the separation of the components.
4. **Detection:** Once separated, the components are detected. This can be done using
various methods depending on the type of chromatography, such as UV-Vis spectroscopy or
mass spectrometry.
5. **Analysis:** The chromatogram, which is a graph of detector response vs. time or volume,
is analyzed to determine the components in the mixture, their identity, and their concentrations.

iii) Identification of components.

Ans Identification of components in a chromatogram involves several key steps:
1. **Retention Time Analysis:** Components elute from the chromatographic column at
different times, known as retention times. By comparing these retention times with those of
known standards, the components can be tentatively identified.
2. **Peak Shape and Size:** The shape and size of the peaks in the chromatogram can provide
clues about the nature of the components. Broad peaks may indicate a mixture, while sharp
peaks suggest a single compound.
3. **Spectral Analysis:** Spectroscopic techniques such as UV-Vis spectroscopy and mass
spectrometry can be used to analyze the peaks. UV-Vis spectroscopy can identify compounds
based on their absorption spectra, while mass spectrometry provides information about the
mass-to-charge ratios of the ions produced, aiding in compound identification.
4. **Chemical Reactions:** Chemical reactions can be carried out on the separated
components to produce characteristic products that aid in identification. For example, a color
reaction with a specific reagent can indicate the presence of certain functional groups.