Chapter 1: Remarks & General Directions

Success as an Analyst

● Must realize that analytical chemistry procedures are not simple

● Manipulative skill (acquired from experience) and following directions is needed for success
● Application of fundamental knowledge of theory is an important objective in studying Quantitative
Pharmaceutical Chemistry (QPC)
● Identification of the reactions taking place during analysis
● Identify which method is dependent
● Have techniques, patience, neatness & accuracy
● Analysis is carried to determine the purity & strength of substances which is used as
medicaments
● Analyst must think throughout the procedure, and must not depend solely on commonsense

Accuracy and Honesty

● All quantitative work must be performed without slight loss & gain of material
● All solutions & precipitates must be covered to protect them from dust
● Every particle of solution or precipitate must be seen as indispensable
● Absolute integrity is much needed
● Operator decides whether the analysis is full of confidence
● It must be stopped if there is no confidence and created new.
● 2 determinations of analytical values are required, and it’s results must be very close
● If values fail to duplicate it means at least 1 value is wrong

Notebook
1. Date
2. Object or Title
3. Experimental Data
4. Reactions
5. Calculations
6. Results
7. Remarks

● Informations must be neat, and arranged in systematic manner

● Date is very needed in all scientific work. Many legal decisions have been lost because of the
failure of an analyst to include date and time
● Experimental data should include complete record: weight, measurements during the time they
are made.
● Recording data on scrap paper is not recommended.
● All reactions must be in structural formulas,
● Using a pocket calculator is recommended to save time, and accuracy. Logarithms could be
alternative too.
● Results must always be in percentages
● Remarks should include unexpected development, error explanation, and comments.

Economy of time
 ● To achieve this, a preliminary study of the experiment is needed to plan how the experiment must
be executed, and keep 2 operations at one time.

Suggestions to save time:

1. Keep desk clean

2. Clean all apparatus immediately
3. Label solutions, filtrates, and precipitates systematically throughout the procedure.
4. Two operations at one time
5. Utilize all time between operations in making calculations and writing up experiments

Cleaning Solution

● Dissolving 200 g of sodium dichromate in 100 ml of water and addition of 1500 ml of sulfuric acid
is a good cleaning solution for glassware.
● Must be stored in a thick-walled glass stoppered bottle; used repeatedly for cleaning glass, and
porcelain until it deposits a large amount of solid material which turns into green.

Wash bottles

● Consists of rubber-stoppered, flat-bottomed flasks of 500-1000 mL capacity with smoothly bent

tubes and a jet made flexible by means of rubber joint.
● Jet should be drawn out to deliver a thin,even stream of liquid.
● There should be two types of wash bottles: 1000 mL and 500 mL capacity for cold and hot water
● Neck of wash bottles for use with hot water. Should be wrapped with asbestos paper or twine.
● To bore a hole, the rubber stopper must be dipped/boil in a strong solution of sodium hydroxide
(2-3 mins) or glycerin before starting to bore
● They are made of Polyethylene. They provide flow of washing solution which ranges from full
stream to single drop

Policeman

● Used to remove particles from wash bottle that are not removable by stream of water
● Should not be used as stirring rod or remain in analytical solutions

Reagents
 ● Reagents under quantitative analysis must be pure
● Reagents that conform to USP and National Formulary (N.F.) should be used in all
assays base on their purpose

Purity and Strength Requirements

● Purity and strength of chemicals of drugs of USP and NF are expressed in percent
● Official requirements of purity and strength pertain only when official methods of assay
are employed

Materials Required
● Statement of materials in exercises is a guide for laboratory instructors, for preparing
adequate supplies for the class.
● Quantities intended are for each sample

Sampling
● Securing a representative sample if the first important consideration in analysis
● There are no fixed rules because sampling depends on the nature of material and the
quantity from which representative sample is taken
● Sample from each package must be examined separately
● Single package sample: contents must be mixed or samples must be from diff. Parts of
the container

● Sample a: Samples of vegetable drugs components are 1 cm or less.

- Powdered or ground substances (core) must be removed in the
container by sampler
- If total weight of drug (X) to be sample is X<100 kg 250 g must be the
official sample
- If X >100kg Quartered method must be done 2 times in which the 2 out
of 4 from the first trial must be rejected, and the remaining 2 must be
combined and mixed carefully as it will be subjected in another trial
again: the second trial. The 2nd trial works exactly the same as the first,
it will be subjected again to the quartering process until two quarters
weigh at least 125 g. If then, the 2 quarters now constitute an official
sample.

● Sample b: samples of vegetable drug components are over 1 cm

- If X<100 kg the official sample must be 500 g
- If X>100 kg the quartered process must be done in the same manner as
sample a until each of the quarters weighs not less than 250 g. If then,
two quarters now constitute an official sample

● Sample C:
 - If X<10 kg quartered process must be followed. The FINAL official
sample must be less than 125 g

● Sample D: alternative to withdrawing of official samples according to methods

a,b,c
- The official sample consists of total amount of a direct purchase made
by officials charged with enforcement of a federal state or municipal food,
and drug acts

● Samples that require drying should be spread on a large watch glass

Calculation of Results and Errors

Source and Nature of Errors

● It is rare that the numerical value of exp. result is directly determined

● Results that agree closely which is acquired from diff. Methods of analysis are a good
indication of the reliability of methods.

2 TYPES OF ERRORS

Indeterminate Errors
- Random error
- Caused by inability of the eye to see slight changes
- Slight variation under same analyst observer, and identical condition.
- These errors being eliminated by the analyst is impossible as it is intangible

Determinate errors
- Personal errors
- Error of method
- Apparatus error

Take Note:

Indeterminate errors shows the relationship between magnitude of error (x or abscissa) and
frequency of its occurence (Y or coordinate). It has the shape of normal frequency distribution
curve, or probability curve called curve of error.
Examination of the curve shows
1. Very large errors are unlikely to happen most of the time
2. Small errors occur more often than large ones
3. Positive and negative errors has same numerical magnitude since the curve is
symmetrical with respect to y axis
Accuracy and Precision

● Accuracy
- Agreement of Mean Value and True Value. It is expressed in terms of error.
- Absolute error: Difference between the mean and true value

Ex. Absolute error = Mean value - True Value

- Relative error: Found by dividing absolute error by true value,

Ex. Absolute error

true Value

● Precision
- Production of data within a series of results
- If the results within the series agree closely, it is said to be precise
- Precision is reported as: Average deviation, standard deviation, range

● Average Deviation
- In terms of use standard deviation is better than average deviation. However this
is acceptable for use in routine analysis.
- Finds differences between individual results, the mean, regardless of sign,
adding these differences, and dividing by number of determinations.It is express
regardless of theirs signs

Absolute errors
Total Samples
- Relative deviation: found by dividing the average deviation by the mean.
Expressed in terms of percentage or as parts as 1000

Relative Average Deviation = Average Deviation x1000

Mean

● Standard Deviation
- Preference measure of precision
- Relative Standard deviation (coefficient of variations)

Relative standard deviation = Standard deviation x 100

Mean

● Range
- Difference between largest and smallest results in measurements

Range = (Largest measurement) −¿(smallest measurement)

● Rejection of result
- The sample result will be rejected if it has shown 4 or more times than the average
deviation. It happens due to mistakes in all. It is rare to happen it occurs in 5/1000

● Significant Figures
- Certain digits of a measurement plus one doubtful digit.
- Zeroes within a number such as 20.04 are significant

● Crucible
- Withstand high temperatures, and suitable for ignition of most drugs and precipitates

● Gooch Filtration Crucible

- Separation precipitates by suction filtration. It has a perforated bottom which is bedded
with a mat of asbestos, making it possible to collect, wash, dry, and weigh a precipitate
in the same crucible.

● Preparation and Use of Gooch Crucible

 - Wash/suspend 0.5 g of asbestos fiber in hydrochloric acid and shake it
then add 100 ml of distilled water in flask. Allow the asbestos to settle and
pour most of the water containing fine fibers. Add 100 ml water and mix it
again. Pour the suspended asbestos mixture into crucible in small
successive portions until a smooth mat not over 1.5 mm thick is obtained.
Cover the asbestos paper with a filter plate. Add a thin layer of asbestos.
Place the prepared crucible on watch glass and dry it for 1 hr in an oven
at 120 to 130 degrees celsius. Allow it to cool in desiccator, then weigh.
Do not stop until the weight of the prepared crucible is constant within
0.0002 g for two successive weighings.

● Fritted Glass crucibles

- These crucibles are useful in analyses where the residue is to be dried constant weight
at temperatures below 150 degrees celsius.

● Filtration and washing precipitate

- The most efficient method of washing a precipitate is by the process of decantation

● Evaporation of liquids
- Best carried out in porcelain dish, as it exposes large surfaces of liquid to the air.
- Volatile Liquids
- indirect heating
Ex. Chloroform
acetone
- Non volatile liquids
- Direct heating
Ex. water 80%
● Transfer of liquid
- Use funnel for transferring liquid (standard solution) to the burette
- 2 Types of Buret
- Acid buret : Acid titrant
- Base Buret: Base titrant

● Dessicator
- Maintain a dry atmosphere for objects that might be affected by moisture or carbon
dioxide. When moisture is affected it grows molds.
- Silica gel is a desiccant or a dehydrating agent. It is important so that molds will not
destroy our objects.