Chemistry Review Group

University of Santo Tomas

Faculty of Pharmacy
Scholia Tutorial Club

REVIEWER: FINAL GRADING PERIOD

ANALYTICAL CHEMISTRY (CHEM 301) LECTURE
Prepared by:
Ser Loisse R. Mortel
Chemistry Review Group

REVIEW PROPER #3:

SOLUBILITY AND
PRECIPITATES
A. DEFINITION AND CONCEPTS
A solution is a homogenous mixture that
consists of a solute and solvent. The
process by which the solute successfully
dissolves in solvent is solvation/
dissolution.
Solubility is highly dependent on polarity
and energy. Polarity is the chemical basis
of solubility that uses the dipoles of the
solute and solvent to predict whether
solvation will take place or not. Energy is
important since even in physical
interactions, enough energy must be used
to overcome the intermolecular forces
between like particles.

B. ksp: SOLUBILITY CONSTANT

Much like equilibrium constants, the same

formula goes to calculating the constant for
solutions. Specifically, the product is/are
the ions, while the reactant is the solute.
Ksp = Product of ions
Recall that in heterogenous equilibrium,
solid products have a concentration
equivalent of 1. Thus, if we add the solute,
the denominator would simply be 1.
NOTE: If an ion has a coefficient, such will
be used as both coefficient and exponent
for the particular ion.
Ex. AB <-> A + 2B, then Ksp = [A][2B] 2
Exercises:
1. CaF2 dissolves into equal portions of
calcium and fluoride ions. Find the Ksp
if each ion has a concentration of 6.24
x 10-6 M.
2. If cuprous hydroxide dissociates into
one cuprous ion and two hydroxide
ions. If its ksp is 2.2 x 10-20, then what
is the concentration of cuprous and
hydroxide ions?

C. MOLAR SOLUBILITY

Molar solubility is defined as the number

of moles of salt that a liter of solution can
handle before it becomes saturated. (n/L or
M)
Solubility is considered as the amount of
grams of ions produced that can saturate a
liter of solution.
Ex. Find molar solubility, ksp and solubility
of AgBr if this salt saturates a liter of
solution with 1.65 x 10-4 grams. MM =
187.8 g/n
Molar solubility = 8.8 x 10-7 M AgBr
Ksp = 7.7 x 10-13
Solubility = 1.65 x 10-4 g/L Ag+ and BrExercises:
1. If barium sulfate dissociates into
barium and sulfate ions, find molar
solubility and solubility if the given
mass to saturate the solution is 2.5 x
10-3 g per liter. MM = 233 g/n
2. Use the exercise problem #2 for Ksp to
find molar solubility and solubility. MM
= 97.5 g/n

D. COMMON-ION EFFECT

In a salt solution that is saturated, the ksp

is equal to the product of the ions
produced. If one of the two ions (usually
the anion) is added, the equilibrium will
have to shift to the direction of the salt,
because of Le Chateliers principle. The
other ion would have to change quantity to
retain the ksp.
Exercise: Given that the solution will form a
precipitate, the Ksp values for AgCl, AgBr
and AgI are 1.6 x 10-10, 7.7 x 10-12, and 8.3
x 10-17, respectively. If silver ions are slowly
added to the solution containing 0.05n of
all these three, which will precipitate first?
Which has the greatest molar solubility?

E. PRECIPITATE PREDICTION AND

RELATIVE SOLUBILITIES

In a salt solution that is saturated, the ksp

will be equal to the product of the ions
produced. If two other salts with the cation
and anion components are mixed together,
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Chemistry Review Group

their resultant ions may be measured and a
new constant may be derived. This is
usually denoted as Q. Because the target
salt would have its own ksp, Q and ksp can
be compared:
If Q > Ksp, precipitation, supersaturation
occurs and will proceed the reduction of
products.
If Q = Ksp, no precipitation, saturation
occurs, equilibrium is achieved and
reaction progress stops.
If Q < Ksp, no precipitation, unsaturation
occurs and will proceed the addition of
products.
Ex. If 0.01M NaOH is added to a liter of
0.1M CuCl2, will Cu(OH)2 precipitate? Ksp =
1.6 x 10-19
Resultant molarities:
MNaOH = (10)(0.01)/1010 = 9.9 x 10-5 M
MCuCl2 = (1000)(0.01)/1010 = 9.9 x 10-3 M
2

A + T ---> Product (till endpoint)

2. Indirect analyte turned into an
intermediate, which reacts with
titrant.
A + some reagent ---> I
I + T ---->Product sufficient to reach
endpoint
3. Back/Residual analyte is flushed with
excess titrant, and a back titrant is
used to cancel out the quantity of
excess titrant.
A + T - BT ---->Product sufficient to reach
endpoint

To compute for concentration of analyte,

-11

Q = [Cu][OH] = 9.7 x 10 ; Q>Ksp, thus

precipitate will form
Exercises:
1. If PbCl2 has a ksp of 1.7 x 10-5, will a
precipitate form if 3g of PbBr2 is added
to a liter of 0.77g of NaCl? MM PbBr 2 =
367.2; MM NaCl = 58
2. What if 0.2M of 250mL PbBr2 was
used in problem #1?

REVIEW PROPER #4:

VOLUMETRIC ANALYSIS
A. DEFINITION AND CONCEPTS

Titrimetry/ Volumetric analysis

determination of the quantity of a certain
substance (analyte) by the help of a
solution of known concentration
(standard/ titrant).
Primary standard solid of assured
purity
Secondary standard liquid standard by
which the concentration is determined by
use of primary standard
To detect that the titration is over, an
indicator is used, which imparts a change
in color in the analyte-standard mixture
when the endpoint is reached.
In endpoint:
amount of analyte = amount of standard
(expressed either in moles or in
equivalents)
Three types:
1. Direct titrant directly to the analyte.

N = equivalents analyte/ mL analyte

(but you dont know equivalents analyte)
- But since eq. analyte = eq. titrant (known
conc.)

N = eq. titrant/ mL analyte

Where:
Eq. titrant = mLtitrant x Ntitrant
(both mL and N of titrant are known)
M = moles analyte/ mL analyte
(but you dont know moles analyte)
- But since moles analyte = moles titrant
(known conc.)

M = moles titrant/ mL analyte

Where:
Moles titrant = mLtitrant x Mtitrant x
molesanaylte/molestitrant
(both mL and N of titrant are known)
(molesanaylte/molestitrant is known as the
reacting ratio for analyte)
In cases of back titration,
mLtitrant = mtitrant in excess mLback titrant
To apply this to knowing the amount of
compound present per sample (percent
purity), we could simply get the grams of
the compound analyzed, then divide it by
total weight of the sample and multiply by
100.
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Chemistry Review Group

% purity = grams of pure compound/
grams sample x 100%
Where:
Grams pure compound = moles x MW; or
Grams pure compound = eq. x eq. wt.

B. CLASSIFICATIONS
1. Neutralization
Acid analyte reacts with basic titrant (or
vice-versa)
Acidimetry titrant used is acid
Alkalimetry titrant used is base
Residual acidimetry/alkalimetry
excess titrant used is acid or base,
respectively
Exercise:
1. 50mL of HCl required 5 grams of Ba(OH)2
to reach endpoint. Calculate the molarity of
HCl.
MW Ba(OH)2 = 171
2. If 12.32 sample was dissolved in 50mL of
0.15N H2SO4 and then followed by 36mL of
0.075N NaOH, calculate the grams of
Mg(OH)2
MW MgO = 40.3
H2SO4 = 98.08
NaOH = 40
3. How much acetic acid (MW = 40) in
percent is there in a 5g sample which
required 30mL of 0.62M KOH solution to
reach the endpoint?
MW KOH = 56.11
Double indicator analysis to determine
amount of several related analytes that
differ from each other only in the relative
amounts of titrant used to neutralize them
for TWO indicators.
Ex. Carbonate, bicarbonate and hydroxide
ions can all be titrated by acid, but they

have differences based on the used acid

per indicator (here, the indicators are
phenolphthalein and methyl orange):
ONE SAMPLE
mLpp = 0 pure CO3-2
mLmo = 0 pure OHmLpp = mLmo pure HCO3mLpp > mLmo mixture of OH- and HCO3mLpp < mLmo mixture of CO3-2 and
HCO3TWO SAMPLE
mLpp = mLmo pure OH2mLpp < mLmo CO3-2 and HCO3mLpp < mLmo CO3-2 and OHmLpp = 2mLmo pure HCO3-2
mLpp = 0 pure CO3(Formulas corresponding to the
interpretation based on one/two-samples
given on a separate paper)
Exercise:
1. One sample: A sample weighing 1.675g
is suspected to be either KOH, K2CO3,
KHCO3 or mixture of these. It was titrated
with 0.15M HCl requiring 15mL to render
solution colorless with PP. After adding MO,
the solution needed 10mL more of the acid.
What is the composition of sample? (Give
the compounds and concentration/s)
MW KOH 56.1
K2CO3 - 138
KHCO3 - 100
2. Two sample: The mixture of the same
substances above but of different
proportions were analyzed. In one portion,
25mL of sample required 13.3 mL 0.23M
HCl with pp as indicator. In another flask
with methyl orange, 25mL of sample
required 45.3mL of the same HCl. What is
the composition of the sample? (Give the
compounds and concentration/s)

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2. Compleximetric

Metal analyte reacts with chelating agent.

EDTA (Ethylenediaminetetraacetic acid) chelating agent used as titrant

Indicators commonly used are Eriochrome Black T and calmagite.
These indicators must have affinity with the metal but LESS THAN the titrant EDTA so that
the moment metals bind with all of EDTA would be the first time the metal binds with the
indicators (= color = endpoint)
NOTES:
- Ratio of EDTA to metal depends on number of species per compound (ex. 1 EDTA per 1
NaCl (because of only 1 Na), 3 EDTA per 1 Na3PO4 (because of 3 Na))
- Complex is result between one group accepting two electrons from one donating group
(the acceptor lacks electrons; metal ions lack electrons = metal ions accept electrons)
WHILE chelate is the result when one donating group binds to several acceptors
- EDTA can donate up to SIX groups, thus it is a chelating agent (can form chelates)
Exercise:
1. A 100g water sample required 25mL of 0.0032M EDTA. Calculate the amount of
magnesium present (in percent).
MW Mg = 24.31
MW EDTA = 292.2g
2. A 25g water sample required 36mL of an EDTA solution that required 2g to be dissolved
in 150mL water. Calculate the amount of magnesium phosphate present (in grams).
MW magnesium phosphate = 262.86
3. Precipitimetric
Titrant is a precipitating agent.
TYPES OF INDICATORS
1. Colored ion FeNH4(SO4)2 (aka ferric alum)
2. Colored secondary/co-precipitate potassium chromate
3. Colored adsorption product dichlorofluorescein (DCF), eosin Y,
tetrabromophenolphthalein ethyl ester (TEE)

METHODS

Thiocyanate
Direct
Volhard
Residual
thiocyanate
Mohr
Uses secondary
ppt
Fajan
Uses adsorption
product

Possible
analytes
Silver and
mercuric salts
Halides

Titrant

Indicator

Endpoint

Ferric alum

Flesh

Ferric alum

Flesh

Halides

Ammonium/potas
sium thiocyanate
Silver nitrate
Thiocyanate
(back titrant)
Silver nitrate

Potassium
chromate

Reddish brown

Halides

Silver nitrate

Adsorption
products

Yellow green,
green, pink

Exercises:
1. 100mL sample of water was titrated with 11.32mL of 0.0201M silver nitrate. Calculate
the percent of hydrogen sulfide in the sample.
MW silver nitrate 169.9
MW hydrogen sulfide 34.1
2. Standardization of KSCN against 0.2514g primary standard silver nitrate required
25.55mL. Calculate the normality of solution.
MW KSCN 97.2
4. Oxidation-Reduction

Reducing analyte reacts with oxidizing titrant (or vice-versa)

- Several methods include permanganate (for hydrogen peroxide), ceric sulfate (for ferric
sulfate and vitamin K), iodimetric (for ascorbic acid), iodometric (for blue vitriol),
dichromate (for alcohol used in breath analyzers to detect drunk persons), bromine,
and nitrite
The only difference of calculations in redox titrations is the reacting ratio.
The ratio of analyte to titrant is based on the number of electrons they can gain (if oxidizing
agent) or lose (if reducing agent). For example,
MnO4- + 5e- ---> 5Mn+2
Since permanganate ion MnO4- gains 5 electrons, it takes 5 molecules of reducing agent per
one permanganate ion.
C2O42- --> 2CO2 + 2eSince oxalate ion C2O42- releases 2 electrons, it takes 2 molecules of oxidizing agent per one
oxalate ion.
Combining them, the ratio becomes 5 C2O4-2/ 2 MnO4Exercise:
1. A 0.5g sample of sodium oxalate required 50mL of potassium permanganate solution.
What is the concentration of potassium permanganate in terms of molarity?
MW potassium permanaganate: 158
MW sodium oxalate: 134

REVIEW PROPER #5: COORDINATION COMPOUND

NOMENCLATURE
A coordination compound is that wherein an electron donor (ligand) binds with an
electron acceptor, usually a metal. Unlike chelates of EDTA, the more numerous in
the case of most coordination compounds are the ligands or complexing agents.
NOMENCLATURE

1. Name the LIGAND. If there are more than one type of ligands, arrange them
alphabetically. Their suffix is -o
2. For anions that end in "-ide"(ex. chloride), "-ate" (e.g. sulfate, nitrate), and "-ite" (e.g.
nirite), change the endings as follows: -ide
-o; -ate
-ato; -ite
-ito
Important exceptions: water is called aqua, ammonia is called ammine, CO is called
carbonyl, and the N2 and O2 are called dinitrogen and dioxygen, respectively.

Anionic
Ligands

Names

Neutral
Ligands

Names

Br-

bromo

NH3

ammine

F-

fluoro

H 2O

aqua

O2-

oxo

NO

Nitrosyl

OH-

Hydroxo

CO

Carbonyl

CN-

cyano

O2

dioxygen

C2O42-

oxalato

N2

dinitrogen

CO32-

carbonato

C5H5N

pyridine

CH3COO-

acetato

H2NCH2CH2NH2

ethylenediamine

3. Greek prefixes are used to to quantify the amount of ligand in the complex, e.g. di-,
tri- and tetra-. If the compound contains polydentate ligands (ie. can attach at more than
one binding site) the prefixes bis-, tris-, tetrakis-, pentakis-, are used instead. (See
examples 3 and 4.) The numerical prefixes are listed in Table 2.

Numb
er

Prefix

Numb
er

Prefix

Numb
er

Prefix

mono

penta
(pentakis)

nona (ennea)

di (bis)

hexa
(hexakis)

10

deca

tri (tris)

hepta

11

undeca

tetra (tetrakis)

octa

12

dodeca

4. Name the ion. Name as is if cation. However, if the complex ion is an anion, the name
of the metal ends with the suffix ate. For example, Co in a complex anion is called
cobaltate and Pt is called platinate. For some metals, the Latin names are used in the
complex anions e.g. Fe is called ferrate (not ironate).
The oxidation state of the metal in the complex is given as a Roman numeral in
parentheses.

Name of Metal

Name in an Anionic Complex

Iron

Ferrate

Copper

Cuprate

Lead

Plumbate

Silver

Argenate

Gold

Aurate

Tin

Stannate

Exercises
Name the following coordination compounds:
1. [Cr(NH3)3(H2O)3]Cl3
2. [Pt(NH3)5Cl]Br3
3. [Pt(H2NCH2CH2NH2)2Cl2]Cl2
4. [Co(H2NCH2CH2NH2)3]2(SO4)3
5. K4[Fe(CN)6]

REVIEW PROPER #6: SPECTROPHOTOMETRY

Spectrophotometry is the quantitative analysis of a compound based on the light that it
absorbs and reflects (does not absorb).
When a beam of light is passed through a sample, all of the light is called the incident
light. Any of the incident light that the sample absorbs is called absorbed light, while
portion not absorbed (and thus, passes through the sample) is called transmitted light/
transmittance.
If the concentration increases, more molecules absorb more light, thus, more absorbed light.
And since any light not absorbed is transmitted, there will be less transmitted light in the
concentrated sample. (As absorbance increases, transmittance decreases and vice-versa).

Common parts of a spectrophotometer.

Beer-Lambert Law states that the absorbance is directly proportional to the
concentration of the solution and the thickness of the sample container the light passes
through.
Thus,

A=lc
Where:
A is absorbance (no units, since A = log10 P0 / P )

or a is the molar absorbtivity/ molar extinction coefficient with units of L mol-1 cm-1

l or b is the path length of the sample - that is, the path length of the cuvette in which the sample is
contained. We will express this measurement in centimetres.
c is the concentration of the compound in solution, expressed in mol L-1

References:

1. Brown, T.L., LeMay, H.E., Bursten, B.E. (2004). Chemistry: The Central Science Ninth
Edition. San Francisco: Pearson Education, Inc.
2. UST Faculty of Pharmacy Department of Biochemsitry. Laboratory Manual in General
Chemistry. University of Santo Tomas.
3. Burdge, J. (2009). Chemistry. New York: McGraw Hill, Inc.
4. Silberberg, M.S. (2009). Chemistry: The Molecular Level of Matter and Change Fifth
Edition. New York: McGraw Hill, Inc.
5. Knevel, A., Digangi, F. (1977). Jenkins Quantitative Pharmaceutical Chemistry. New York:
McGraw Hill, Inc.
6. www.chemistry.wustl.edu