Chem Biol Lesson 4-6

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LESSON 04: Calculations Used in

Analytical Chemistry
Unit 01: A review on the basic concepts of measurement
SI Units
Kilogram (kg) – A measurement of mass of a substance.
Meter (m) – A measurement of length, perimeter or distance. The meter was redefined by
international agreement in 1983 as the length of the path traveled by light in a vacuum in
1/299,792,458 of a second.
Moles (mol) – A unit of measurement for amount of substance. A mole of a substance or a mole
of particles is defined as containing exactly 6.02214076×1023 particles, which may be atoms,
molecules, ions, or electrons. In short, 1 mol contains 6.02214076×1023 of the specified particles.
Second (s) – The base unit of time. This was historically defined as 1⁄86400 of a day from the
division of the day first into 24 hours, then to 60 minutes and finally to 60 seconds each.
Kelvin (K) – A measure of temperature on an absolute scale, meaning that 0 kelvin is relative to
zero heat content.
Ampere (A) – A measure of electric current, which is closely related to the measure of charge,
Coulomb flowing through a conducting medium per second.
Candela (cd) – the base unit of luminous intensity of radiation such as light; that is, luminous
power per unit solid angle emitted by this point light source in a fixed direction.
Conversions and the Factor Label Method
Quantities in science have both magnitude (the number) and unit (the dimension). The factor
label method, sometimes called dimensional analysis, is a solving technique using conversion
factors to transform units from one system to the another.

You might also be familiar with the “cancellation” of units.

The factor can be multiplied to a magnitude because it is equivalent to 1. Given that the two
quantities are equal, such as 2.54cm = 1inch,
Sample Problem 1: Given that 1ft = 12in and 1cm = 2.54cm, Convert 0.02515 ft3 to cm3.

Sample Problem 2: Convert 3.25 lb/ft3 into g/cm3 knowing that 2.2 lb = 1 kg.
Difference of Mass
from Weight

• Mass is the quantity or amount of a


substance being measured.
• Weight is a measure of the Earth’s
gravitational force exerted on a quantity of
matter. Weight is one way to measure mass.
In other words, we can measure the quantity
of a substance by measuring the Earth’s
gravitational effect on it.
• Technically, however, analytical quantities are
mass quantities and not weight quantities.
Counting Using Moles
• For solids we often weigh the material, for liquids we get the volume, and for
contained gases we often find its pressure.
• Moles of a substance is also an expression of quantity
• A mole is a very large number; 1 mole is equal to 6.022 x 1023 particles – this
number is also known as the Avogadro’s Number (NA).
• For example, the molecular mass of Glucose C6H12O6 is:
Counting Using Moles
• What is the mass in grams of Na+ (22.99 g/mol) in 25.0 g of Na2SO4 (142.0 g/mol)?
Counting Using Moles
Determine the number of moles in 78.5g of potassium benzoate (C7H5KO2).
LESSON 04: Calculations Used
in Analytical Chemistry
Unit 02: Expressions of Concentration
Expressions of Concentration
In wet chemistry, we often use a background substance – a solvent, that often takes up most
of the volume of our liquid. Furthermore, solubility through a solvent is a limited space, and a
solution can already be saturated at the smallest amounts of solute.
1. Percent by Volume (%v/v) – Volume/volume percentage (v/v percent) is a measure of the
concentration of a substance in a solution.

2. Molarity (M) – also called Molar concentration, is a measure of the concentration of a


chemical species, in terms of a solute within a solution. A solution with a concentration of 1
mol/L is said to be 1 molar, commonly designated as 1 M.
Expressions of Concentration
3. Molality (m) - Molality is a measure of number of moles of solute present in 1 kg of
solvent. This contrasts with the definition of molarity which is based on a specified volume of
solution. Molality is used on physical chemistry because of mathematical convenience.
commonly used unit for molality in chemistry is mol/kg. A solution of concentration 1 mol/kg
is also sometimes denoted as 1 molal.

4. Parts per Million (ppm) – A concentration of a solution that contained 1 g solute and
1,000,000 mL solution would create a very small percentage concentration.

If water is the solvent (having a density of 1g/mL):


Expressions of Concentration
p-Function (p[X]) – The concentration of a species in terms can be expressed in its pfunction, or p-
value. The p-value is the negative logarithm (to the base 10) of the molar concentration (M) of that
species.
Sample Problem 5:

Calculate the molar concentration of ethanol in an aqueous solution that contains 2.30 g of
C2H5OH (46.07 g/mol) in 3.50 L of solution.
Sample Problem 6:
58 cm3 of ethyl alcohol was dissolved in 400 cm3 of water to form 454cm3 of a solution of
ethyl alcohol. Calculate the percentage by Volume of ethyl alcohol in water.
Sample Problem 7:
A 5 gallon volume of benzene is accidentally added to an aquifer whose volume is 3.79×108⋅L.
If homogeneous mixing is assumed, what is the ppm concentration with respect to benzene?
(Density of benzene = 0.874g/mL ; 1 US gal = 3.78541)
Sample Problem 8:
Calculate the p-value for each ion ( [H+], [Na+], [Cl-] ) in a solution that is 2.00 x 10-3 M in
NaCl and 5.4 x 10-4 M in HCl.
Density and Specific Gravity
Matter is something that has mass and occupies space – or in other words, volume.
Therefore, in this definition you could also see that all matter has density since it all has both
mass and volume. The density of a substance is its mass per unit volume and often
symbolized as ρ, the Greek letter rho. Mathematically, density is defined as mass divided by
volume:

Density is an intensive property in that increasing the amount of a substance does not
increase its density; rather it increases its mass. Its reciprocal is occasionally called its
specific volume, a term sometimes used in thermodynamics. The density of a material would
vary with different temperatures and pressure

Specific gravity is the ratio of the density of the material to that of a standard material,
usually water which has a density of 1g/mL.
If water is the reference substance, it will just be equal to Density
1. Density of Regular Solids – If we wanted to
measure the density of a rectangularly shaped
solid, we would measure the mass in grams and
then measure the dimensions of the solid—the
length, width, and height—in centimeters to find
the volume. The density would be calculated
from these measurements.
2. Density of Irregularly Shaped Solids – The
density of an irregularly shaped solid is usually
determined by measuring the mass and then
measuring the volume of liquid that it displaces.
The volume of liquid in a graduated cylinder is
measured before the object is submerged and
then measured again with the object
submerged.
3. Density of Liquids – To determine the density
of a liquid, the mass in grams of a measured
volume of liquid in milliliters is determined. The
density is calculated from these measurements.
The volume may be measured by a variety of
devices, such as a graduated cylinder, pipet, or
burette. Very precise determinations of volume
are measured with pycnometers
4. Bulk Density – Bulk density, or the apparent density, is the total mass per unit of
total volume. It is not an intrinsic property of a material since it varies with the size
distribution of the particles and their environment. The porosity of the solid and the
material with which the pores, or voids, are filled also affect the bulk density. Only
for a single nonporous particle that the true density equals the bulk density.
Sample Problem 9
A sample of quartz sand weighs 2.65 g and occupies a volume of 2.0 cm3. What is its bulk
density?

Sample Problem 10
A chunk of metal has a mass of 4.8 g when weighed in air. Using the displacement method,
the initial and final volumes of the water submerged by the metal were 7.0mL to 9.0mL
respectively. What is the density of the metal chunk?
LESSON 04: Calculations Used in
Analytical Chemistry
Unit 03: Preparation of Standard Solutions through the Direct Method
The Standard Solution
Titrant is the solution of known concentration that is added to a solution containing
an analyte of unknown concentration in a titration process. A solution of known
concentration is known as a standard solution. According to Skoog, et. al., the
ideal standard solution that is used in titrimetric analysis should have the following
characteristics:
a. Be sufficiently stable so that it is necessary to determine its concentration only
once;
b. React rapidly with the analyte so that the time required between additions of
reagent is minimized;
c. React more or less completely with the analyte so that satisfactory end points
are realized;
d. Undergo selective reaction with the analyte that can be described by a balanced
equation.
Preparation of the Standard Solution through
the Direct Method
A carefully determined mass of a primary standard is dissolved in a
suitable solvent and is carefully diluted to a desired volume in a
volumetric flask. A primary standard is an ultrapure compound that
serves as a reference material for quantitative analysis.
Calculations Involving the Preparation of Standard Solutions
through the Direct Method

Problem 01: Describe the preparation of 500 mL of 0.3000 M AgNO3 from the primary standard grade
solid.
Problem 02: Describe the preparation of 50.0 mL of 0.05M Ag+ from the solution prepared
above
Problem 03: Describe the preparation of 200.0 mL of 5.00% (w/v) aqueous CuSO4 from a 0.500 M
CuSO4 solution.
Given: a reagent of 0.500 M CuSO4 solutionvolume of solution to be prepared = 200 mL
concentration of the solution to be prepared = 5.00% (w/v)
Required: Description of the method of preparation for 200.0 mL of 5.00% (w/v) CuSO4 solution
Problem 04: Describe the preparation of 2.00 L of 0.355 M NaOH from the concentrated
commercial reagent [50% NaOH (w/w), specific gravity = 1.525]

Given: a concentrated NaOH solution volume of solution to be prepared = 2.00 L concentration of the
solution to be prepared = 0.355 M
Required: Description of the method of preparation for 2.00 L of 0.355 M NaOH solution, [50% NaOH
(w/w), specific gravity = 1.525].

Answer:
Dilute 37.2 mL of 50% (w/w) NaOH solution to 2.00 liters.
Problem 05: Describe the preparation of 2.00 L of a solution that is 15.0 ppm K+ starting with solid
K4Fe(CN)6.
Given: a solid K4Fe(CN)6. volume of solution to be prepared = 2.00 L concentration of the solution to
be prepared = 15.0 ppm K+
Required: Description of the method of preparation 2.00 L of a solution that is 15.0 ppm K+
LESSON 05: Sampling,
Standardization and Calibration
Unit 01: Sampling and Sample Preparation
Kind of analysis based on sample size
1. Macro analysis – this kind of analysis is for samples with masses greater than 0.1 g.
2. Semi-micro analysis – this method is used in handling samples with masses that range
from 0.01 to 0.1 g.
3. Micro analysis – analysis of samples with masses of 10-4 to 10-2 g.
4. Ultra-micro analysis – for very minute sample masses which is less than 10-4 g.
The constituent concentration that is found in the sample can also dictate the kind of analysis to
be done. Below are the types of constituents:
1. Major constituent – these are constituents that are present in the sample at 1 to 100% by mass
2. Minor constituent – constituents that are present in 0.01 to 1% of the sample
3. Trace constituent – these are constituents that are present in the sample between the
concentration of 100 ppm to 1 ppb
4. Ultratrace constituent – these are constituents that are present in amounts that is smaller than
1 ppb.
Sampling
We call the process of getting a representative fraction of a sample from its source as
sampling. In sample collection we call samples that are chosen for analysis as sample
increments, the collection of this sample increments is typically called by chemists as the gross
sample.
Statistically, sampling aims to:
1. Obtain a mean analyte concentration that is an unbiased estimate of the population mean.
2. Obtain a variance in the measured analyte concentration that is an unbiased estimate of the
population variance so that valid confidence limits can be found for the mean, and various
hypothesis tests can be applied

These sampling goals all lead to what we call as random sampling which is a kind of sampling
that utilizes randomization procedure to obtain a sample. An example of this is labeling
samples from 1 to 100 without proper labeling and randomly choosing 5 numbers between 1 to
100 as the samples for analysis.
Representative Samples
The other designations for samples designates them according to their stage in the
laboratory procedure, namely: bulk sample, primary sample, secondary sample,
subsample, laboratory sample, and test sample. These terms are used when a
sample of a bulk system is divided, possibly a number of times, before actually
used in an analysis.
For example, a water sample from a well may be collected in a large bottle (bulk
sample or primary sample) from which a smaller sample is acquired by pouring
into a vial to be taken to the laboratory (secondary sample, subsample, or
laboratory sample) and then poured into a beaker (another secondary sample or
subsample) before a portion is finally carefully measured into a flask (test sample)
and diluted to make the sample solution. The problems associated with sampling
are unique to every individual situation. The analyst simply needs to take all
possible variations into account when obtaining the sample, so that the sample
taken to the laboratory truly does represent what it is intended to represent.
Gross sample
Gross sample size is determined by:
(1) uncertainty that can be tolerated between the
composition of the gross sample and that of the whole
(2) degree of heterogeneity of the whole, and
(3) level of particle size at which heterogeneity begins
Sample Problem # 1
A column-packing material for chromatography consists of a mixture of two types of particles.
Assume that the average particle in the batch being sampled is approximately spherical with a
radius of about 0.5 mm. Roughly 20% of the particles appear to be pink in color and are known to
have about 30% by mass of a polymeric stationary phase attached (analyte). The pink particles
have a density of 0.48 O/'(=. The remaining particles have a density of about 0.24 O/'(= and
contain little or no polymeric stationary phase. What mass of the material should the gross sample
contain if the sampling uncertainty is to be kept below 0.5% relative? (retrieved from: Skoog,2015)
Sampling for homogeneous
mixtures of liquids and
gasses

make sure that it is homogeneous entirely,


which can be achieved by stirring it well
before sampling
Sampling Particulate solids
As what we previously discussed, random sampling is the most
convenient way of sampling particulate solids.

Sampling Metals and Alloys


The usual sampling done for metals and alloys is through sawing,
drilling and milling into the samples. However, the it is important that
the drilling should be able to reach the interior of the sample as well.
Now, it may seem that the gross product is the highlight of this
lesson, however, in a real chemical analysis, it is the laboratory
sample that is of interest to us
LESSON 05: Sampling,
Standardization and Calibration
Unit 02: Standardization and Calibration
• Calibration and standardization are considered to be pivotal in all
chemical analysis. Calibration describes the relationship between
the analytical response and the concentration of the analyte.
• Chemical standards are what relates the two to each other.
Chemical standards come as a purified analytical grade reagent or
standardized classical quantitative method.
External standard Calibration is by far the most common calibration
technique. It involves the preparation of standard solutions separately
from the sample. These standards are used by the instrument to
function which is obtained from analysis of the instrument response
as a function of the known analyte concentration. If the analysis
requires high specificity and selectivity, three or more standard
solutions are followed, but in some cases a two-point calibration is
sufficient.
Generally, a plot of instrument response versus known analyte
concentrations is used to produce a calibration curve, sometimes
called a working curve.
Errors in External Calibration
Ideal blanks - are substances that are identical to the sample but
with the absence of the analyte. However, the preparation of ideal
blanks is time consuming and nearly impossible.
solvent blank - this blank contains the same solvent in which the
sample was dissolved.
reagent blank - is also used, which in this case doesn’t only
contain the solvent at which the sample was dissolved, but also
contains all the reagents that was used during sample
preparation.
To avoid systematic errors in calibration, standards must be
accurately prepared, and their chemical state must be identical to
that of the analyte in the sample. The standards should be stable in
concentration, at least during the calibration process.
Minimizing Errors in Analytical Procedures
A. Separation
Separating the analyte from possible interferences from the
sample is a very important method to ensure that errors are
minimized during data analysis. Techniques such as filtration,
precipitation, dialysis, solvent extraction, volatilization, ion
exchange, and chromatography are all very useful in ridding the
sample of potential interfering constituents. Separation
techniques are kind of a double-edge sword, it can help in
getting rid of interferences but it can also cause loss of precious
analyte. With this concern in mind, new technologies have been
invented such as flow-injection or chromatography with split of
split-less injection systems.
B. Saturation, Matrix Modification, and Masking
The saturation method involves adding the interfering species to all
the samples, standards, and blanks so that the interference effect
becomes independent of the original concentration of the interfering
species in the sample.
By adding a matrix modifier which is not itself an interfering species,
in samples, standards, and blanks in sufficient amounts with the aim
of making the analytical response independent of the concentration
of the interfering species.
Some chemists, do masking, by adding a masking agent, which reacts
selectively with the interfering species to form a complex that does
not interfere.
C. Dilution and Matrix Matching
By using the dilution method, we lower down the concentration of the
entire sample, this is only useful if the interfering species produces no
significant effect below a certain concentration level.
So, the interference effect is minimized simply by diluting the sample.
Contrary to the dilution method is the matrix-matching method
attempts to duplicate the sample matrix by adding the major matrix
constituents to the standard and blank solutions. For example, in the
analysis of seawater samples for a trace metal, the standards can be
prepared in a synthetic seawater containing Na+, K+, Cl-, Ca2+,
Mg2+and other components.
D. Internal Standard Methods
An internal standard is a reference species, chemically and physically
similar to the analyte, that is added to samples, standards, and
blanks. In the internal standard method, a known amount of a
reference specie is added to all samples, standards and blanks.
When this method is done, the response signal is no longer the
response of the analyte, but rather the ratio between the response of
the analyte with the reference specie.
E. Standard Addition Methods
We use the method of standard additions when it is difficult or
impossible to duplicate the sample matrix. In general, the sample is
“spiked” with a known amount or known amounts of a standard
solution of the analyte.
In the single-point standard addition method, two portions of the
sample are taken. One portion is measured as usual, but a known
amount of standard analyte solution is added to the second portion.
The responses for the two portions are then used to calculate the
unknown concentration assuming a linear relationship between
response and analyte concentration
(Skoog, 2015).
LESSON 06: Errors in
Chemical Analysis
Unit 01: Errors in Chemical Analysis
Errors
Two types of errors in the analytical laboratory
• “Determinate Errors”
• “Indeterminate errors”

Determinate errors are also called systematic errors. These are errors that were known to have
occurred, or at least were later known to have occurred, in the course of the lab work. It may come
from avoidable sources, such as contamination, wrongly calibrated instruments, reagent
impurities, instrumental malfunctions, poor sampling techniques, and errors in calculations. If the
error was a calculation error, it must be recalculated. If avoidable determinate errors results from
laboratory work are known to have occurred, then the faulty result must then be rejected.
Determinate errors may also arise from unavoidable sources. An error that is known to have
occurred but was unavoidable is called a “bias”. Such an error occurs each time a procedure is
executed, and thus its effect is usually known and a correction factor can be applied.
Errors
Two types of errors in the analytical laboratory
• “Determinate Errors”
• “Indeterminate errors”

Indeterminate errors are also known as random errors. These are errors that are not specifically
identified and are therefore impossible to avoid. Unlike for determinate errors, results arising from
such errors cannot be immediately rejected or compensated since the errors cannot be specifically
identified. Statistical analysis is applied to determine the rejection of a result; categorizing whether
it is far enough “off-track” to be rejected. An established quality limits for the answers are derived
from any given method. If a sample is within these limits, the data is still considered as “good”.
Review of Elementary Statistics
1. Mean – In the case in which a given measurement on a sample is repeated a number of times,
the average of all measurements is called the mean. It is calculated by adding together the
numerical values of all measurements and dividing this sum by the number of measurements. In
this text, we give the mean the symbol m. The true mean, or the mean of an infinite number of
measurements (the entire population of measurements), is given the symbol m, the Greek letter
mu.
2. Deviation – How much each measurement differs from the mean is an important number and is
called the deviation. A deviation is associated with each measurement, and if agiven deviation
is large compared to others in a series of identical measurements, the proverbial red flag is
raised. Such a measurement is called an outlier. Mathematically, the deviation is calculated as
follows:

in which d is the deviation, m is the mean, and e represents the individual experimental
measurement. The bars refer to absolute value, which means the value of d is calculated without
regard to sign.
3. Standard deviation – The most common measure of the dispersion of data around the mean
is the standard deviation:

The term n is the number of measurements, and n – 1 is referred to as the number of degrees of
freedom. The term s represents the standard deviation. The significance of s is that the smaller
it is numerically, the more precise the data (the more the measurements are “bunched” around
the mean). For an infinite number of measurements (where the mean is m), the standard
deviation is symbolized as s (Greek letter sigma) and is known as the population standard
deviation. An infinite number of measurements is approximated by 30 or more measurements.
4. Relative Standard deviation – The most common measure of the dispersion of data around
the mean is the standard deviation. One final deviation parameter is the relative standard
deviation (RSD).

It is calculated by dividing the standard deviation (s) by the mean (m) and then multiplying by
100. Relative standard deviation relates the standard deviation to the value of the mean and
represents a practical and popular expression of data quality.
The Normal Distribution
For an infinite data set, a plot of frequency of
occurrence vs. the measurement value yields
a smooth bell-shaped curve. It is referred to
as bell-shaped because there is equal drop-
off on both sides of a peak value, resulting in
a shape that resembles a bell. The peak value
corresponds to m, the population mean. This
curve is called the normal distribution curve
because it represents a normal distribution of
values for any infinitely repeated
measurement.
Precision and Accuracy
Precision refers to the repeatability of a measurement. If you repeat a given measurement
over and over and these measurements deviate only slightly from one another, within the
limits of the number of significant figures obtainable, then we say that the data are precise,
or that the results exhibit a high degree of precision. The mean of such data may or may not
represent the real value of that parameter. In other words, it may not be accurate.

Accuracy refers to the correctness of a measurement, or how close it comes to the correct
value of a parameter. For example, if an analyst has an object that he or she knows weighs
exactly 1.0000 g, the accuracy of a laboratory balance (weight measuring device) can be
determined. The object can be weighed on the balance to see if the balance will read 1.0000
g.
If it is established that a measuring
device provides a value for a known
sample that is in agreement with the
known value to within established
limits of precision, that device is said
to be calibrated. Thus, calibration
refers to a procedure that checks the
device to confirm that it provides the
known value. The calibration curve
ensures that the read-outs follow a
simple linear relationship within the
course of a very small chosen range.
Statistical Control
Using Control Charts
A given device, procedure, process, or method is
usually said to be in statistical control if numerical
values derived from it on a regular basis (such as
daily) are consistently within 2 standard deviations
from the established mean, or the most desirable
value. As we learned in previously, such numerical
values occur statistically 95.5% of the time. Thus if,
say, two or more consecutive values differ from the
established value by more than 2 standard
deviations, a problem is indicated because this
should happen only 4.5% of the time, or once in
roughly every 20 events, and is not expected two or
more times consecutively. The device, procedure,
process, or method would be considered out of
statistical control, indicating that an evaluation is in
order.

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