EXPRESSIONS OF CONCENTRATIONS OF
SOLUTIONS VOLUME PERCENTAGE (v/v)%
The concentration of a solution
- is defined as the amount of solute present
in a given quantity of solvent.
Solutions
- are often referred to as being concentrated
or dilute. These two terms are very
general.
Concentrated
- indicates that there is a lot of solute
dissolved in the solvent (perhaps the
solution is near to being saturated)
Dilute
- indicates that a small amount of solute is
dissolved in the solvent, we often need to
be exact with quantities in chemistry.
COMMON EXPRESSIONS OF
CONCENTRATIONS OF SOLUTIONS
MOLE FRACTION (X)
Mole fraction
- is a unit of concentration, defined to be
equal to the number of moles of a
component divided by the total number of
moles of a solution.
- Because it is a ratio, mole fraction is a
unitless expression.
- The mole fraction of all components of a
solution, when added together, will equal 1.
- It is used in a variety of calculations, but
most notably for calculating partial
pressures.
MASS PERCENTAGE (w/w)%
Calculations for solid samples are based
on weight. The most common way of expressing
the results of macro determinations is to give the
weight of analyte as a percent of the weight of
sample (weight/weight basis).
The weight units of analyte and sample are
the same.
Mass percentage
- is also referred to by similar names such as
percent mass, percent weight,
weight/weight percent and other variations
on this theme.
The most common symbol for mass
percentage is simply the percent sign, %,
although more detailed symbols are often used
including %mass, %weight, and (w/w)%.
It is most frequently used by chemists and
are popular concentration units for consumer
products.
Liquid volumes over a wide range of
magnitudes are conveniently measured using
common and relatively inexpensive laboratory
equipment.
The concentration of a solution formed by
dissolving a liquid solute in a liquid solvent is
therefore often expressed as a volume
percentage, %vol or (v/v)%:
MASS-VOLUME PERCENTAGE (m/v)%
“Mixed” percentage units, derived from
the mass of solute and the volume of solution, are
popular for certain biochemical and medical
applications.
A mass-volume percent is a ratio of a
solute’s mass to the solution’s volume expressed
as a percentage. The specific units used for solute
mass and solution volume may vary, depending on
the solution.
For example, physiological saline solution,
used to prepare intravenous fluids, has a
concentration of 0.9% mass/volume (m/v),
indicating that the composition is 0.9 g of solute
per 100 mL of solution.
TRACE CONCENTRATIONS
Very low solute concentrations are often
expressed using appropriately small units such as
parts per million (ppm) or parts per billion (ppb).
Like percentage (“part per hundred”) units,
ppm and ppb may be defined in terms of masses,
volumes, or mixed mass-volume units.
There are also ppm and ppb units defined
with respect to numbers of atoms and molecules.
On the other hand, Clinical chemists sometimes
prefer to use the unit milligram percent (mg%)
rather than ppm for small concentrations. This is
defined as milligrams of analyte per 100g of
sample.
Both ppm and ppb are convenient units for
reporting the concentrations of pollutants and
other trace contaminants in water.
Concentrations of these contaminants are
typically very low in treated and natural waters,
and their levels cannot exceed relatively low
concentration thresholds without causing adverse
effects on health and wildlife.
MOLARITY AND FORMALITY
Both molarity and formality express
concentration as moles of solute per liter of
solution (or millimoles per milliliter, mmol/ml).
 There is, however, a subtle difference
between molarity and formality.
Molarity is the concentration of a particular
chemical species in solution.
Formality, on the other hand, is a
substance’s total concentration in solution
without regard to its specific chemical form.
There is no difference between a
substance’s molarity and formality if it dissolves
without dissociating into ions. The molar
concentration of a solution of glucose, for
example, is the same as its
formality.
Concentration most often used in a
chemical laboratory.
Molar concentrations are used so
frequently that a symbolic notation is often used to
simplify its expression in equations and writing.
The use of square brackets around a species
indicates that we are referring to that species’
molar concentration.
Thus, [Na+] is read as the “molar
concentration of sodium ions.”
Moreover, the liter is an impractical unit for
the relatively small quantities encountered in
titrations, and we normally work with milliliters and
millimoles in analytical chemistry. This is what your
buret reads..
NORMALITY
Although molarity is widely used in
chemistry, some chemists use a unit of
concentration in quantitative analysis
called normality (N).
A one-normal solution contains one
equivalent per liter (eq/L or meq/ml). An equivalent
represents the mass of material providing
Avogadro’s number of reacting units.
A reacting unit is a proton or an electron.
The number of equivalents is given by the number
of moles multiplied by the number of reacting units
per molecule or atom.
The equivalent weight (in g/equiv) is the
formula weight divided by the number of reacting
units or factor (f). The equivalent weight depends
on the chemical reaction. It may vary most often in
redox reactions, when different products are
obtained.
Normality is most often encountered in
situations that involve the reactions of acids with
bases.
MOLALITY
Molality (m) is used in thermodynamic
calculations where a temperature independent unit
of concentration is needed.
A one-molal solution contains one mole
per 1000g of solvent. The molal concentration is
convenient in physicochemical measurements of
the colligative properties of substances, such as
freezing point depression, vapor pressure
lowering, and osmotic pressure because
colligative properties depend solely on the number
of solute particles present in solution per mole of
solvent.
Molal concentrations are not temperature
dependent as molar and normal concentrations
are (since the solution volume in molar and normal
concentrations is temperature dependent). \
By using the solvent’s mass in place of its
volume, the resulting concentration becomes
independent of temperature.
p – FUNCTIONS
Sometimes it is inconvenient to use the
previous concentration units. For example, during
a reaction a reactant’s concentration may change
by many orders of magnitude.
If we are interested in viewing the progress
of the reaction graphically, we might wish to plot
the reactant’s concentration as a function of time
or as a function of the volume of a reagent being
added to the reaction.
When working with concentrations that
span many orders of magnitude, it is often more
convenient to express the concentration as a
p-function. The p-function of a number X is written
as pX and is calculated as pX = – log (X)
DILUTION OF SOLUTIONS
Dilution is the process whereby the
concentration of a solution is lessened by the
addition of solvent.
For example, we might say that a glass of
iced tea becomes increasingly diluted as the ice
melts. The water from the melting ice increases
the volume of the solvent (water) and the overall
volume of the solution (iced tea), thereby reducing
the relative concentrations of the solutes that give
the beverage its taste.
Dilution is also a common means of
preparing solutions of a desired concentration. By
adding solvent to a measured portion of a more
concentrated stock solution, we can achieve a
particular concentration of dilute solutions.
 For example, we may prepare a dilute HCl
solution from concentrated HCl to be used for
titrations (following standardization).
Or, we may have a stock standard solution
from which we wish to prepare a series of more
dilute standards. The millimoles of stock solution
taken for dilution will be identical to the millimoles
in the final diluted solution,
Remember, V1C1 = V2C2
Where: V1 = initial volume
C1 = initial concentration
V2 = final volume
C2 = final concentration
CONVERSION OF CONCENTRATION UNITS
The units of concentration most frequently
encountered in analytical chemistry are molarity,
weight percent, volume percent,
weight-to-volume percent, parts per million,
and parts per billion.
By recognizing the general definition of
concentration, it is easy to convert between
concentration units.
COLLIGATIVE PROPERTIES OF SOLUTIONS
Solution has physical properties; Physical
properties can be divided into two categories.
1. Extensive properties
- (such as mass and volume)
- depend on the size of the sample.
2. Intensive properties
- (such as density and concentration)
- are characteristic properties of the
substance;
- they do not depend on the size of the
sample being studied.
This section introduces a third category
that is a subset of the intensive properties of a
system. This third category, known as colligative
properties, can only be applied to solutions. By
definition, one of the properties of a solution is a
colligative property if it depends only on the ratio
of the number of particles of solute and solvent in
the solution, not the identity of the solute.
Very few of the physical properties of a
solution are colligative properties.
Measurements of these properties for a
dilute aqueous solution of a non-ionized solute
such as urea or glucose can lead to accurate
determinations of relative molecular masses.
Alternatively, measurements for ionized
solutes can lead to an estimation of the
percentage of ionization taking place.
These are properties of solutions that
depend on the number of molecules in a given
volume of solvent and not on the
properties/identity (e.g size or mass) of the
molecules.
Colligative properties include: relative
lowering of vapor pressure; elevation of boiling
point; depression of freezing point and osmotic
pressure.
A. FREEZING POINT DEPRESSION IN
SOLUTIONS
The freezing point of pure water is 0°C, but
that melting point can be depressed by the adding
of a solvent such as a salt.
The use of ordinary salt (sodium chloride,
NaCl) on icy roads in the winter helps to melt the
ice from the roads by lowering the melting point of
the ice.
A solution typically has a measurable lower
melting point than the pure solvent.
The following figures were found in a
published report, but have not been checked out in
detail. A 10% salt solution was said to lower the
melting point to -6°C (20°F) and a 20% salt
solution was said to lower it to -16°C (2°F).
A more formal treatment of freezing point
depression is given by Ebbing. The freezing
point depression, ΔTf, is a colligative property of
the solution and colligative property of the solution,
and is defined as freezing point of pure solvent
minus the freezing point of solution, giving the
formula = ΔTf = Tfs – Tfp
Where: ΔTf = freezing point elevation
Tfs = freezing point of solution
Tfp = freezing point of pure solvent
And also since ΔT is proportional to the
concentration, molality (m) of the solution Cm,
given the equation ΔTf α Cm
ΔTf = Kf Cm
Where K, is called the
freezing-point-depression constant
A pleasant application of the freezing point
depression is in the making of homemade ice
cream. The ice cream mix is put into a metal
container which is surrounded by crushed ice.
Then salt is put over the ice to lower its
melting point.
The melting of the solution lowers the
equilibrium temperature of ice/water solution to the
melting point of the solution; this gives a
temperature gradient across the metal container
into the water-ice solution which is lower than 0°C.
The heat transfer of the ice cream mix allows it to
freeze.
B. BOILING POINT ELEVATION IN
SOLUTIONS
The boiling point of pure water is 100°C,
but that boiling point can be elevated by the
adding of a solute such as a salt.
A solution typically has a measurably
higher boiling point than the pure solvent. A
treatment of boiling point elevation is given by
Darrell Ebbing. The boiling point elevation ΔTb is
a colligative property of the solution, and is defined
as boiling point of solution minus the boiling point
of pure solvent, giving the formula
ΔTb = Tbs – Tbp
Where: ΔTb = boiling point elevation
Tbs = boiling point of solution
Tbp = boiling point of pure solvent
And since ΔTb, is proportional to the
concentration, molality (m) of the solution Cm,
giving the equation
ΔTb α Cm
ΔTb = KbCm
Where Kb is called the
boiling-point-elevation constant.
Solutions may be produced for the purpose
of raising the boiling point and lowering the
freezing point, as in the use of ethylene glycol in
automobile cooling systems. The ethylene glycol
(antifreeze) protects against freezing by lowering
the freezing point and permits a higher operating
temperature by raising the boiling point.
The figure below shows the consequences
of the fact that solutes lower the vapor pressure of
a solvent. The solid line connecting points B and C
in this phase diagram contains the combinations of
temperature and pressure at which the pure
solvent and its vapor are in equilibrium. Each point
on this line therefore describes the vapor pressure
of the pure solvent at that temperature. The dotted
line in this figure describes the properties of a
solution obtained by dissolving a solute in the
solvent. At any given temperature, the vapor
pressure of the solvent escaping from the solution
is smaller than the vapor pressure of the pure
solvent. The dotted line therefore lies below the
solid line. The decrease in the vapor pressure of
the solvent occurs when a solute is added to the
solvent causes an increase in the boiling point and
decrease in the melting point of the solution.
According to the figure, the solution can’t
boil at the same temperature as the pure solvent.
If the vapor of the solvent escaping from the
solution is smaller than the vapor pressure of the
pure solvent at any given temperature, the solution
must be heated to a higher temperature before it
boils. The lowering of the vapor pressure of the
solvent that occurs when it is used to form a
solution therefore increases the boiling point of the
liquid.
When the phase diagrams were
introduced, the triple point was defined as the only
combination of temperature and pressure at which
the gas, liquid, and solid can exist at the same
time. The figure above shows that the triple point
of the solution occurs at a lower temperature than
the triple point of the pure solvent. By itself, the
change in the triple point is not important. But it
results in a change in the temperature at which the
solution freezes or melts. To understand why, we
have to look carefully at the line that separates
solid and liquid regions in the phase diagram. This
line is almost vertical because the melting point of
a substance is not very sensitive to pressure.
Adding a solute to a solvent doesn’t
change the way the melting point depends on the
pressure. The line that separates the solid and
liquid regions of the solution is therefore parallel to
the line that serves as the same function for the
pure solvent. This line must pass through the tripe
point for the solution; however the decrease in the
triple point that occurs when a solute is dissolved
in a solvent therefore decreases the melting point
of the solution.
The change in vapor pressure that occurs
when solute dissolves in a solvent leads to
changes in the melting point and the boiling point
of the solvent as well. For the change in vapor
pressure a colligative property, which depends
only on the relative number of solute and solvent
particles, the changes in the boiling point and the
melting point of the solvent are also colligative
properties.
PRESSURE AND ITS MEASUREMENT
Pressure is defined as the force per unit
area. P = F/A
Pressure is measured in units of
atmosphere (atm) or mmHg or torr.
The SI unit of pressure is pascal (Pa) or
kilopascal (kPa). Its equivalents are as follows:
1 Pa = 1 N/m2 = 1 kg/m.s2 = 1 J/m3
 1 kPa = 1,000 Pa
1 bar = 100 kPa = 100,000 Pa
1 atm= 760 torr = 760 mmHg = 101.325
kPa = 101,325 Pa = 14.7 psi
C. VAPOR PRESSURE LOWERING
As an example of the limited set of physical
properties (colligative properties) of a solution, let’s
consider what happens to the vapor pressure of
the solvent when we add a solute to form a
solution.
Consider P0 as the vapor pressure of the
pure liquid, the solvent and P as the vapor
pressure of the solvent after a solute has been
added.
ΔP = P0 – P
Where: ΔP = vapor pressure lowering P
0 = vapor pressure of the pure liquid, or
solvent
P = vapor pressure of the solvent in a
solution
When the temperature of a liquid is below
its boiling point, we can assume that the only
molecules that can escape from the liquid to gas
are those that lie near the surface of the liquid.
When a solute is added to the solvent,
some of the solute molecules occupy the space
near the surface of the liquid, as show in the figure
below. When a solute is dissolve in a solvent, the
number of solvent molecules near the surface
decreases, and the vapor pressure of the solvent
decreases.
This has no effect on the rate at which
solvent molecules in the gas phase condense to
form a liquid. But it decreases the rate at which the
solvent molecules in the liquid can escape into the
gas phase. As a result, the vapor pressure of the
Solvent escaping from a solution should be
smaller than the vapor pressure of the pure
solvent.
P < P0
Vapor pressure of the Vapor pressure of
solvent above a solution the pure solvent
Between 1887 and 1888, Francois-Marie
Raoult showed that the vapor pressure of a
solution is equal to the mole fraction of the solvent
times the vapor pressure of the pure liquid.
P = Xsolvent P0
Vapor pressure of the Vapor pressure of
solvent above a solution the pure solvent
This equation, which is known as Raoult’s
law, is easy to understand. When the solvent is
pure, and the mole fraction of the solvent is equal
to 1, P is equal to P0. As the mole fraction of the
solvent become smaller, the vapor pressure of the
solvent escaping from the solution also becomes
smaller.
Let’s assume, for the moment, that the
solvent is the only component of the solution that
is volatile enough to have a measurable vapor
pressure. if this is true, the vapor pressure of the
solvent escaping from the solution.
Raoult’s law suggests that the difference
between the vapor pressure of the pure solvent
and the solution increases as the mole fraction of
the solvent decreases.
The change in the vapor pressure that
occurs when a solute is added to a solvent is
therefore a colligative property. If it depends on the
mole fraction of the solute, then it must depend on
the ratio of the number of particles of solute to
solvent in the solution but not the identity of the
solute.
As a summary, we can say that pressure of
the solvent over a solution (P) is the vapor
pressure of pure solvent (P0) times the mole
fraction of the solvent in the solution X1.
P = X1P0
X1 + X2 = 1
X1 = 1 – X2
P = ( 1 – X2 ) P0
P = P0 – X2P0
P0 – P = Xsolute P0
P = P0 – P = Xsolute0 (solute is non-volatile)
(both components are volatile)
P = P1 + P2
P1 = X1P1 0 P2 = X2P20
P = (X1P10) + (X2P20)
D. OSMOTIC PRESSURE (π)
In 1784, the French physicist and
clergyman Jean Antoine Nollet discovered that a
pig’s bladder filled with a concentrated solution of
alcohol in water expanded when it was immersed
in water. The bladder acted as a semi- permeable
membrane, which allowed water molecules from
moving in the other direction. Movement of one
component of a solution through a membrane to
dilute the solution is called osmosis, and the
pressure this produces osmotic pressure (π).
The same year that Raoult discovered the
relationship between the vapor pressure of a
solution and the vapor pressure of a pure solvent,
Jacobus Henricus Van Hoff found that the
osmotic pressure of a dilute solution (π) obeyed
an equation analogous to the ideal gas equation.

This equation suggests that osmotic
pressure is another example of colligative
property, because this pressure depends on the
ratio of the number of solute particles to the
volume of the solution -n/V- not the identity of the
solute particles. It also reminds us of the
magnitude of osmotic pressure.
According to this equation, a 1.00 M
solution has an osmotic pressure of 22.4 atm at
0oC.
This means that a 1.00 M solution should
be able to support a column of water 670 inches,
or almost 56 feet, tall!
Biologists and biochemists often take
advantage of osmotic pressure when they isolate
the components of a cell.
When a cell is added to an aqueous
solution that contains a much higher concentration
of ions than the liquid within the cell, water leaves
the cell by flowing through the cell membrane until
the cell shrinks so that the membrane breaks.
Alternatively, when a cell is placed in a
solution that has a much smaller ionic strength,
water pours into the cell, and the cell expands until
the cell membrane bursts.
CHEMICAL EQUILIBRIUM
Many chemical processes may themselves
are reversible. That is, the products of a reaction
may themselves interact, thus settling up a
reversible process.
Under constant conditions, such as
temperature and concentration, such
interaction of products will result in an equilibrium.
Such an equilibrium is a dynamic one. That is, the
equilibrants are constantly interacting even though
at any instant there exists a given mass ratio
among the substances involved. A knowledge of
the concentrations of the reacting substance at
equilibrium is essential in the industries which
depend upon a chemical change to obtain a
marketable product.
Chemical equilibria may involve
substances in the solid, liquid, or gaseous states.
All plant and animal tissues depend upon specific
chemical equilibria to function properly.
A reaction is said to be reversible when the
products that are formed react to reform the
reactants. Initially, the reaction proceeds in the
forward direction, favoring the formation of
products. When the concentration of the products
become sufficiently high, the products react to
form the reactants again. This backward reaction
continues until a state of balance called dynamic
equilibrium is reached.
Although the chemical reaction is in a state
of dynamic equilibrium, it does not mean that
reaction has ceased.
Rather, when an equilibrium is of a
dynamic nature, the rate of the forward reaction is
equal to the rate of the backward reaction, i.e., the
rate of formation of products is equal to the rate at
which these products are dissociated to form the
Reactants.
A good example of a dynamic reversible
process is the evaporation and condensation of
water in a closed vessel.
At the start of the evaporation process,
water molecules escape from the liquid state into a
vapor state. Since the process takes place in a
sealed container, the water vapor molecules are
trapped inside and build up gradually. When the
container becomes saturated with water vapor, the
water vapor condenses into a liquid until a state of
dynamic equilibrium is established.
An equilibrium state can be disturbed by
the application of a stress, e.g., a change in the
concentration of reactants or products, or both, or
any change in pressure or temperature.
According to Le Chatelier's rule, the
application of a stress to a system at equilibrium
will cause the equilibrium to shift so as to minimize
the stress, and ultimately reestablish equilibrium.
For equilibrium systems, an increase in
the concentration of the reactants or a decrease in
the concentration of the products favors a forward
shift, causing the formation of more products. An
increase in the concentration of products, or a
decrease in the concentration of the reactants shift
the equilibrium backward, causing the formation of
more reactants.
The effect of pressure on an equilibrium
system is better observed in gases. If pressure is
increased in a gaseous system, it creates a
proportionate decrease in volume, causing the
equilibrium to shift toward the formation of less
gaseous particles.
Consider the following equilibria:
Equilibrium A: A(g) + 2B(g) ⇄ AB2(g)
Equilibrium B: X(g) + Y(g) ⇄ 2C(g) + D(g)
Equilibrium C: Z2(g) + T2(g) ⇄ 2 ZT(g)
Increasing the pressure for the above
systems will cause:
● a forward shift for equilibrium A, because
the forward reaction causes the formation
of only one gaseous particle as compared
to three in the reactants; In the above reactions, Sf represents the
● a backward shift for equilibrium B, rate of the forward reaction, and Sr is the rate of
because the backward reaction causes the the reverse reaction. At equilibrium, Sf = Sr. The
formation of less gaseous particles (3 equilibrium constant for the above reaction would
gaseous particles in the product, and 2 be:
gaseous particles in the reactants); and where K is called the equilibrium
● no effect on equilibrium C, because there constant. The notation [X] represents the molar
is an equal number of gaseous reactants concentration (in moles per liter or M) of the
and products in equilibrium C. chemicals involved. A more general equilibrium
equation would be:
Decreasing the pressure of the above
systems will produce the opposite effect for each
equilibrium system.
Not all reactions give similar responses to
changes in temperature. For exothermic
reactions, an increase in temperature favors the
reaction that causes absorption of heat, in this
example, the backward reaction. Since these
reactions release heat, the application of more
heat will shift the equilibrium in the direction where
heat absorption takes place.
A + B ⇄ C + heat
For endothermic reactions, an increase
in temperature favors the forward reaction. These
reaction absorbs heat and the application of heat The value of K for any given reaction is
will shift the equilibrium toward heat absorption. essentially a constant at a given temperature.
A + B + heat ⇄ C Note that the value of K is independent of
the concentrations of the reacting substances. Any
MOLECULAR EQUILIBRIA change in the concentrations of the reacting
THE EQUILIBRIUM CONSTANT substances by the addition or removal of reacting
substances will shift the equilibrium and maintain
Chemical equilibria involve two opposing the K constant for that temperature.
processes occurring simultaneously and at the It is evident that the addition of C or D as to will
same rate. By rate of reaction is the amount of shift the equilibrium to the left and the removal of
reacting material converted to products in a given C or D will shift the equilibrium to the right, in
period of time. Amounts are usually given in either case the value of K remaining constant.
moles, and time in seconds. Evidently, when K is large, C and D
A chemical equilibrium may be represented predominate, when K is small, A and B
by the general equation: predominate.

IONIC EQUILIBRIA IN SOLUTION

THE IONIZATION CONSTANTS OF ACIDS AND
BASES
Certain covalent compounds such as
HC2H3O2 and NH4OH undergo partial ionization
when in water solution. An equilibrium is thus
established between ionized and non-ionized
molecules. The equilibrium constant principle may
therefore be applied to such ionizations equations.
For example, for the ionization equations of
acetic acid, HC2H3O2 and ammonium hydroxide,
NH4OH, the equilibrium expressions would be:
Ka is called the acid constant, and Kb the
basic constant.
THE SOLUBILITY PRODUCT
The solubility product principle applies to
saturated solutions of very slightly soluble
electrolytes. Such electrolytes may be assumed to
be 100 percent ionized in solution, the ions being
in equilibrium with the undissolved solid according
to the equation:
where Ksp is called the solubility product
constant. The solubility product is therefore the
product of the concentrations of the ions
originating from a salt. Evidently, if the product of
the concentrations of the ions is less than Ksp, the
solution is unsaturated. If two solutions are mixed,
one of which contains Ba+2 ions and the other
SO4–2 ions, precipitation of BaSO4 will occur
only if [Ba+2] [SO4–2] Ksp for BaSO4 is 1.1 x 10
–10 at 25 0C.
The solubility product involves the use of
very small quantities. However, such quantities are
quite significant and find wide application in
quantitat ive analysis.
STATISTICS AND ERRORS OF A
CHEMICAL ANALYSIS
Although data handling normally follows
the collection of analytical data, a knowledge of
statistical analysis will be required as you
perform experiments in the laboratory.
Also, statistical analysis is necessary to
understand the significance of the data that are
collected and thus sets limits on each step of the
analysis.
Experimental design (including required
sample size, measurement accuracy, and number
of analyses needed) relies on a proper
understanding of what the data represent.
ACCURACY VS. PRECISION
Precision describes the agreement among
several results obtained in the same way. It is
readily determined by simply repeating the
measurement on replicate samples. Precision is a
measure of the spread of data about a central
value and may be expressed as the range, the
standard deviation, or the variance. Precision is
commonly divided into two categories:
repeatability and reproducibility.
Repeatability is the precision obtained
when all measurements are made by the same
analyst during a single period of laboratory work,
using the same solutions and equipment.
Reproducibility, on the other hand, is the
precision obtained under any other set of
conditions, including that between analysts, or
between laboratory sessions for a single analyst.
Since reproducibility includes additional sources of
variability, the reproducibility of an analysis can
be no better than its repeatability. The
deviation from mean, di, is how much xi, the
individual result, deviates from the mean, x̅.
Accuracy, on the other hand, indicates the
closeness of the measurement to the true or
accepted value and is expressed by the error. It
measures the agreement between a result and the
accepted value. It is often more difficult to
determine because the true value is usually
unknown.
 An accepted value must be used instead.
Accuracy is expressed in terms of either absolute
or relative error:
1. ABSOLUTE ERROR: The absolute error of
a measurement is the difference between
the measured value and the true value. If
the measurement result is low, the sign is
negative; if the measurement result is
high, the sign is positive.
2. RELATIVE ERROR: The relative error of a
measurement is the absolute error divided
by the true value. Relative error may be
expressed in percent, parts per
thousand, or parts per million, depending
on the magnitude of the result.
TYPES OF ERRORS IN EXPERIMENTAL DATA
The precision of a measurement is readily
determined by comparing data from carefully
replicated experiments. Unfortunately, an estimate
is not as easy to obtain. To determine accuracy,
we have to know the true value, and this value
is ordinarily exactly what we are seeking in the
analysis. It is tempting to assume that if we know
the answer precisely, we also know it accurately.
There is a danger if we do that assumption.
Every chemical analysis has an error. Three
general types of errors occur in lab
measurements: random error, systematic error,
and gross errors.
A. RANDOM ERROR
Random (or indeterminate) errors
are caused by uncontrollable fluctuations in
variables that affect experimental results.
For example, air fluctuations occurring as
students open and close lab doors cause
changes in pressurE readings.
Random errors represent the
experimental uncertainty that occurs in
any measurement. These errors are
revealed by small differences in successive
measurements made by the same analyst
under virtually identical conditions, and
they cannot be predicted or estimated.
These accidental errors will follow a
random distribution; therefore,
mathematical laws of probability can be
applied to arrive at some conclusion
regarding the most probable result of a
series of measurements. A sufficient
number of measurements result in evenly
distributed data scattered around an
average value or mean. This positive and
negative scattering of data is characteristic
of random errors.
It is beyond the scope of this text to
go into mathematical probability, but we
can say that indeterminate (RANDOM)
errors should follow a normal
distribution, or Gaussian curve.
The estimated standard deviation
(the error range for a data set) is often
reported with measurements because
random errors are difficult to eliminate.
Also, a "best-fit line" is drawn
through graphed data in order to "smooth
out" random error. It is apparent that there
should be few very large errors and that
there should be an equal number of
positive and negative errors.
Indeterminate ( RANDOM) errors
really originate in the limited ability of the
analyst to control. Some random errors
stem from the intrinsic nature of things.
Sometimes, by changing conditions, some
unknown error will disappear. Of course, it
will be impossible to eliminate all possible
random errors in an experiment, and the
analyst must be content to minimize them
to a tolerable or insignificant level.
B. SYSTEMATIC ERROR
Systematic (or determinate)
errors are instrumental, methodological, or
personal mistakes causing "lopsided" data,
which is consistently deviated in one
direction from the true value. In other
words, they are characterized by a
systematic deviation from the true value;
that is, all the individual measurements are
either too large or too small. A positive
determinate error results in a central
value that is larger than the true value, and
a negative determinate error leads to a
central value that is smaller than the true
value. Both positive and negative
determinate errors may affect the result of
an analysis, with their cumulative effect
leading to a net positive or negative
determinate error. It is possible, although
not likely, that positive and negative
determinate errors may be equal, resulting
in a central value with no net determinate
error.
Determinate errors may be divided
into four categories: sampling errors,
method errors, measurement errors, and
personal errors.
 Systematic errors can be
identified and eliminated after careful
inspection of the experimental methods,
cross-calibration of instruments, and
examination of techniques.
Determinate errors may be divided
into four categories: sampling errors,
method errors, measurement errors, and
personal errors.
1. Sampling Errors: We introduce
determinate sampling errors when
our sampling strategy fails to
provide a representative sample.
This is especially important when
sampling heterogeneous
materials. For example,
determining the environmental
quality of a lake by sampling a
single location near a point source
of pollution, such as an outlet for
industrial effluent, gives misleading
results. In determining the mass of
a U.S. penny, the strategy for
selecting pennies must ensure that
pennies from other countries are
not inadvertently included in the
sample. Determinate errors
associated with selecting a
sample can be minimized with a
proper sampling strategy.
2. Methodological Errors:
Determinate method errors are
introduced when assumptions
about the relationship between the
signal and the analyte are invalid.
For example, methods in which
Smeas is the mass of a precipitate
containing the analyte (gravimetric
method) assume that the sensitivity
is defined by a pure precipitate of
known stoichiometry. When this
assumption fails, a determinate
error will exist. Method errors
involving sensitivity are
minimized by standardizing the
method, whereas method errors
due to interferents present in
reagents are minimized by using a
proper reagent blank. Method
errors due to interferents in the
sample cannot be minimized by a
reagent blank. Instead, such
interferents must be separated from
the analyte or their concentrations
determined independently.
3. Measurement / Instrumental
Errors: Analytical instruments and
equipment, such as glassware and
balances, are usually supplied by
the manufacturer with a statement
of the item’s maximum
measurement error, or tolerance.
For example, a 25-mL volumetric
flask might have a maximum error
of ±0.03 mL, meaning that the
actual volume contained by the
flask lies within the range of
24.97–25.03 mL. Although
expressed as a range, the error is
determinate; thus, the flask’s true
volume is a fixed value within the
stated range. Determinate
measurement errors can be
minimized by calibration. A pipet
can be calibrated, for example, by
determining the mass of water that
it delivers and using the density of
water to calculate the actual volume
delivered by the pipet. Although
glassware and instrumentation can
be calibrated, it is never safe to
assume that the calibration will
remain unchanged during an
analysis. Many instruments, in
particular, drift out of calibration
over time. This complication can be
minimized by frequent recalibration.
4. Personal Errors: Finally, analytical
work is always subject to a variety
of personal errors, which can
include the ability to see a change
in the color of an indicator used to
signal the end point of a titration;
biases, such as consistently
overestimating or underestimating
the value on an instrument’s
readout scale; failing to calibrate
glassware and instrumentation; and
misinterpreting procedural
directions. Personal errors can be
minimized with proper care.
C. GROSS ERROR
Gross errors are caused by experimenter
carelessness or equipment failure. These
"outliers" are so far above or below the true value
that they are usually discarded when assessing
data. The "Q-Test" is a systematic way to
determine if a data point should be discarded.
EFFECTS OF SYTEMATIC ERRORS
Systematic errors are measures of the
agreement between the measured quantity and
the true value. In analytical results, these may
either be constant or proportional:
1. CONSTANT ERROR: It refers to a
difference between the target value and the
assayed value. It is independent of sample
concentration or the size of the quantity
measured. It exists when there is a
continual difference between the
comparative method and the test method
regardless of the concentration.
2. PROPORTIONAL ERROR: Also known as
slope or percent error, it results in greater
deviation from the target value due to
higher sample concentration. It exists when
the difference between the test method and
the comparative method value is
proportional to the analyte concentration. In
other words, it increases or decreases in
proportion to the size of the sample taken
for analysis. A common cause of
proportional errors is the presence of
interfering contaminants in the sample.
ERROR AND UNCERTAINTY
Analytical chemists make a distinction
between error and uncertainty.
Error is the difference between a single
measurement or result and its true value. In other
words, error is a measure of bias. As discussed
earlier, error can be divided into determinate
(systematic) and indeterminate(random)
sources. Although we can correct for determinate
error, the indeterminate portion of the error
remains. Statistical significance testing provides a
way to determine whether a bias resulting from
determinate error might be present.
Uncertainty expresses the range of
possible values that a measurement or result
might reasonably be expected to have. Note that
this definition of uncertainty is not the same as that
for precision. The precision of an analysis, whether
reported as a range or a standard deviation, is
calculated from experimental data and provides an
estimation of
indeterminate error affecting measurements.
Uncertainty accounts for all errors, both
determinate and indeterminate, that might affect
our result. Although we always try to correct
determinate errors, the correction itself is subject
to random effects or indeterminate errors.
ABSOLUTE AND RELATIVE UNCERTAINTY
1. Absolute uncertainty expresses the
margin of uncertainty associated with a
measurement. If the estimated uncertainty
in reading a calibrated buret is + 0.02 ml.,
we say that + 0.02 ml. is the absolute
uncertainty associated with the reading.
2. Relative uncertainty compares the size of
the absolute uncertainty with the size of its
associated measurement. The relative
uncertainty of a buret reading of is a
dimensionless quotient:
● Relative uncertainty = Absolute
uncertainty / Magnitude of
measurement
The percent relative uncertainty is simply
● Percent Relative uncertainty =
Relative uncertainty x 100 %
If the absolute uncertainty in reading a
buret is constant at the percent relative uncertainty
is 0.2% for a volume of 10 mL and 0.1% for a
volume of 20 mL.
STATISTICAL MEASURES AND DATA
HANDLING
IN ANALYTICAL CHEMISTRY
It is seldom easy to estimate the reliability
of experimental data. Nevertheless, we must make
such estimates whenever we collect laboratory
results because data of unknown quality are
worthless. On the other hand, results that are not
especially accurate may be of considerable value
if the limits of uncertainty are known. This can be
measures through proper data handling and
calculating some statistical measures of a
given set of analytical data.
MEASURES OF CENTRAL TENDENCY
The idea of a single “typical” value
representative of a sample or a population is a
very useful one in the analysis of statistical data.
Since there are many ways of calculating such a
value, with its own advantages and disadvantages,
statisticians use the more generic term measures
of central tendency here. These measures of
central tendency are single numerical values
which are intended to indicate the center or middle
region of the distribution of values.
A. MEAN
 The mean is calculated by adding up all the
data values and dividing by the number of data (n).
This formula can be concisely represented using
summation notation.
1. x̅ARITHMETIC MEAN – usually referred to
the average of a set of values or
measurements that is computed by the
sum of all measurements divided by the
total number of observations in a given
population. This can be the sample mean (
) or the population mean (μ).
2. WEIGHTED MEAN – may be computed
from a frequency distribution by
determining the sum of the data values
multiplied by their respective weights or
frequencies divided by the sum of the
frequencies themselves. Here, a data with
a relatively higher frequency will contribute
more to the average than another data
value with a relatively lower frequency. If all
the frequencies are set equal to 1, the
ordinary arithmetic mean results
ADVANTAGES OF THE MEAN
1. It is a measure that can be calculated and
is unique.
2. It is useful for performing statistical
procedures such as comparing the means
from several data sets.
DISADVANTAGES OF THE MEAN
1. It is affected by extreme values that are not
representative of the rest of the data.
B. MEDIAN
The median is the midpoint of the data
after being ranked (sorted in ascending order).
There are as many numbers below the median as
above the median. If there are an odd number of
data points, the median is the median value. If
there are an even number of data, the median is
half way between the two middle values. An
advantage of the median is that it avoids the
sensitivity to a few highly unusual observations.
STEPS IN DETERMINING THE MEDIAN
1. Sort the data values into an ascending
order.
2. Find the depth of the median by the
formula (n+1)/2
3. Based on the depth of the median, the
median is taken to be the middle element
of the sorted list (if it is odd) or the mean of
the two middle elements (if it is even).
MEASURES OF SPREAD / VARIABILITY
Variability refers to how "spread out" a
group of scores or values is. The terms variability,
spread, and dispersion are synonyms, and refer
to how spread out a distribution is. Just as in the
section on central tendency we discussed
measures of the center of a distribution of scores,
in this chapter, we will discuss measures of the
variability of a distribution. The three frequently
used measures of variability are the range,
variance and standard deviation.
A. RANGE ( R )
The range is the simplest measure of
variability to calculate, and one you have probably
encountered many times in your life. The range is
simply the highest score minus the lowest score.
B. VARIANCE
Variability can also be defined in terms of
how close the scores in the distribution are to the
middle of the distribution. Using the mean as the
measure of the middle of the distribution, the
variance is defined as the average squared
difference of the scores from the mean.
The variance of a sample (s2) of a set of
measurements is defined to be the average of the
squares of the deviations of the measurements of
the mean (x) divided by (n-1).
C. STANDARD DEVIATION
The standard deviation is simply the
square root of the variance. It is an especially
useful measure of variability when the distribution
is normal or approximately normal because the
proportion of the distribution within a given number
of standard deviations from the mean can be
calculated.
The standard deviation of a sample (s) of a
set of measurements is equal to the positive
square root of the variance.
COEFFICIENT OF VARIATION
The coefficient of variation (CV) is the
ratio between the standard deviation and its
corresponding mean. It reflects the variation in a
distribution relative to the mean. The result is
usually expressed in percentage (%). This
measure is used to compare standard deviations
when the units are different for the two variables
being compared. It allows us to compare the
dispersions of two different distributions if their
means are positive. The coefficient of variation for
a distribution can be calculated to compare the
values obtained with another distribution. The
greater dispersion corresponds to the value of the
coefficient of greater variation. The coefficients of
variation for different distributions are compared,
and the distribution with the largest coefficient of STEPS IN DETERMINING THE CONFIDENCE
variation value has the greatest relative variation. INTERVAL AND LIMITS
ADVANTAGES OF THE COEFFICIENT OF 1. Determine the mean (x or μ) and the
VARIATION standard deviation (s or σ ) from the
1. The coefficient of variation is useful because given replicate measurements.
the standard deviation of data must always 2. Calculate for the confidence interval
be understood in the context of the mean of using the formula:
the data. Student’s t values is a statistical tool used
2. The coefficient of variation is a unitless most frequently to express confidence intervals
number. This allows CVs to be compared to and to compare results from different experiments.
each other in ways that other measures, like This is tabulated and usually given in problems.
standard deviations or root mean squared 3. Determine the confidence limits by
residuals, cannot be. calculating the lowest (–) and the highest
3. For comparison between data sets with (+) confidence intervals.
different units or widely different means, one
should use the coefficient of variation
instead of the standard deviation.
DISADVANTAGES OF THE COEFFICIENT OF
VARIATION
1. When the mean value is close to zero, the
coefficient of variation will approach infinity
and is hence sensitive to small changes in
the mean.
2. Unlike the standard deviation, it cannot be
used to construct confidence intervals for
the mean.

CONFIDENCE LIMITS
X̅ In most quantitative chemical analysis,
the true value of the mean μ cannot be
determined because a huge number of
measurements (approaching infinity) would be
required.
With statistics, however, we can establish
an interval surrounding the experimentally
determined mean within which the population
mean μ is expected to lie within a certain
degree of probability. This interval is known as the
confidence interval.
Sometimes, the limits of the interval are
called confidence limits. For example, we might
say that it is 99 % probable that the true population
mean for a set of potassium measurements lies in
the interval 7.25 + 0.15 % K. Thus, the probability
that the mean lies in the interval from 7.10 to 7.40
% K is 99 %. The size of the confidence interval,
which is computed from the sample standard
deviation, depends on how well the sample
standard deviation s estimates the population
standard deviation σ. If s is a good estimate of σ,
the confidence interval can be significantly
narrower than if the estimate of σ is based only a
few measurement values.