Volumetric

Analysis

Term 1:
Week 3
 Outline

• The Mole
• Avogadro’s constant
• Reacting masses
• Concentration
• Titration
• Standard solutions
• Rough and accurate titres
• Significant figures
• Back titration
How do we measure quantity of substance?

Before: Hydrogen = 1 g mol-1 1H 2H 3H - isotopes

Now: Carbon-12 (12C) = 12 g mol-1

Element Symbol Relative atomic mass
Carbon-12 12C 12.000
Carbon C 12.011
Copper Cu 63.54
Hydrogen H 1.008
Magnesium Mg 24.312
 Avogadro constant

The number of atoms in exactly 12

grams of isotope 12C (1 mole) was
defined as Avogadro constant.
NA = 6.02 × 1023

Amadeo Avogadro

Macroscopic scale Atomic scale

 The Mole
• The relative atomic mass in grams of all elements
contains the same number of atoms.
One mole (n) is the amount of substance
which contains the same number of particles
(atoms, molecules or ions) as there are atoms
in 12.00g of isotope 12C.
 Molar mass
The mass of one mole of a substance is called
molar mass (A or Mr).
• Molar mass numerically equals to the atomic
mass but in units of gram per mole (g mol-1).

 Molar mass of a molecular substance is equals to

its molecular mass.
Molar mass (or atomic weight for elements)

Atomic weight
in g/mol
 General sequence of calculation
• The relationship below allow us to connect
the laboratory scale with the atomic scale
using our standard dimensional analysis.
Elementary
Molar Avogadro’ units of A
Grams of Moles of
mass of A s Number (atoms,
substance A substance A
molecules,
ions)

During conversion take care of units (grams, not kilograms)

for mass and magnitude (×1023) for elementary units!
 Example of calculation:
The amount of substance n (in mole) and the number of
atoms (N) contained in it, are related to the Avogadro’s
number:
N/n = 6.02×1023 mol−1

Example: 2 g of magnesium ribbon

Amount of substance (n) =
mass (m) / molar mass (A)
= 2 / 24.312 = 0.08226 mol

Number of atoms (N) =

amount of substance (n) × Avogadro’s number (NA)
= 0.08226 × 6.02×1023 = 4.9523×1022 atoms
 Stoichiometry
• Stoichiometry translates as “measure of the elements”.
Stoichiometry is a quantitative relationship among the species
involved in a chemical process in a molecular or molar amounts.
• Practically, stoichiometry is used for converting chemical formulas
and equations that represent individual atoms, molecules, and
formula units into to the laboratory scale units which are
milligrams, grams of these substances.

aA + bB cC
1g ?g ?g
Stoichiometry
Grams of Molar Moles of Moles of Molar Grams of
Chemical
substance mass of A substance substance mass of B substance
equation
A A B B
 Stoichiometry

Magnesium ribbon with a mass of

2 g was burned in air. What is the
mass of obtained MgO?

2 Mg(s) + O2(g) 2 MgO(s)

nMg = mMg / AMg = 2 / 24.312 = 0.08226 mol of Mg

2 mol of Mg produces 2 mol of MgO. So, 0.08226 mol of

Mg will produce 0.08226 mol of MgO.

mMgO = nMgO x AMgO = 0.08226 x 40.312 = 3.31607g of MgO

 Limiting and excess reagents

Limiting
Excess
 Example:

m(H2) = 20g
m(O2) = 99.8g
m(H2O) = ?
2 H2 + O2 2 H2O
Solution:

1 𝑚𝑜𝑙 𝐻2
𝑛 𝐻2 = 20.0g 𝐻2 × = 9.92 𝑚𝑜𝑙 𝐻2
2.016 𝑔 𝐻2

1 𝑚𝑜𝑙 𝑂2
𝑛 𝑂2 = 99.8g 𝑂2 × = 3.122 𝑚𝑜𝑙 𝑂2
32.0 𝑔 𝑂2
 Finding limiting reagent
2H2 + O2 2 H2O
Initial (mol) 9.92 3.12

Stoichiometric 2 1
coefficient

Compare 4.96 3.12

Excess reagent Limiting reagent

(remained unreacted) (completely consumed)
 2H2 + O2 2 H2O
Initial (mol) 9.92 3.12

Consumed (mol) -6.24 -3.12 +6.24

Result (mol) 3.68 0 6.24

Excess reagent Limiting reagent

(remained unreacted) (completely consumed)

18.04 𝑔 𝐻2 𝑂
m 𝐻2 𝑂 = 6.24 mol 𝐻2 𝑂 ×
1 𝑚𝑜𝑙 𝐻2 𝑂
= 112.57 𝑔 𝐻2 𝑂
 Solution and concentration

A solution is a homogeneous mixture in

which the molecules or ions of the
components freely intermingle.
• The solvent is the medium into
which the solutes are mixed or
dissolved.
• A solute is any substance
dissolved in solvent.
Concentration is the ratio of the amount of
solute to the amount of solution.
 Molarity
• Chemists usually measure the concentration of solution
as the number of moles of solute per cubic decimetre of
solution. Concentration in mol dm-3 is also called
molarity.
1 cubic decimetre (dm ) = 1000 cm = 1 litre
3 3

Example: 11.7 g of NaCl was

dissolved in 500 ml of water. What is
the concentration of solution?

n = m/A = 11.7/58.5 = 0.2 mole of NaCl

M = n/V = 0.2/0.5 = 0.4 mol dm-3

 Dilution
• Laboratory chemicals are usually purchased in
concentrated form and must be diluted with
water (made less concentrated) before being
used.
• During dilution, the number of moles of solute
remains constant.
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓
𝑑𝑖𝑙𝑢𝑡𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 × 𝑀𝑑𝑖𝑙𝑢𝑡𝑒 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑒𝑑 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 × 𝑀𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑒𝑑
𝑡𝑜 𝑏𝑒 𝑝𝑟𝑒𝑝𝑎𝑟𝑒𝑑 𝑡𝑜 𝑏𝑒 𝑢𝑠𝑒𝑑

Moles of solute in Moles of solute in

dilute solution concentrated solution

𝑉𝑑𝑖𝑙 × 𝑀𝑑𝑖𝑙 = 𝑉𝑐𝑜𝑛𝑐 × 𝑀𝑐𝑜𝑛𝑐

 Reacting masses

What if we don’t know the

concentration of HCl?
 Titration
• Titration (volumetric analysis) is a common laboratory
method of quantitative chemical analysis that is used to
determine the unknown concentration of a known
reactant.
Meniscus
TITRANT = STANDARD
SOLUTION (concentration
39.3 mL
& volume are known)

ANALYTE = TITRAND
(unknown concentration)
NaOH, 1 M (titrant)

pH indicator
HCl, 25 mL, 1 M (analyte) (colour of the solution changes
+ pH indicator
depending on the pH)
 Neutralization

reactants products

product of reaction

pH indicator
substance which changes the colour of the solution
depending on the concentration of H+ ions ( pH)
 pH indicators
A common way to detect the equivalence point in an acid-base
titration is to add an pH indicator, a compound that changes color as
an acidic solution becomes basic (equivalence point), or vice versa.
Color on Acidic Color on Basic
Indicator
Side Side
Methyl Violet Yellow Violet
Bromophenol
Yellow Blue
Blue
Methyl Orange Red Yellow
Methyl Red Red Yellow
Litmus Red Blue
Bromothymol
Yellow Blue
Blue
Phenolphthalein Colorless Pink
Alizarin Yellow Yellow Red
 Titration
• Read the bottom of the meniscus, while your
eye is level with it. The meniscus can be seen
more easily against a white background.

Number of titration Rough Accurate 1 Accurate 2 Accurate 3

Initial burette reading (cm3) 10.0 10.0 10.0 20.0
Final burette reading (cm3) 35.3 35.0 35.1 45.0
Titre (cm3), Vin - Vfin 25.3 25.0 25.1 24.9
 Rough and accurate titres
• Rough titration is the trial process (first titration)
in order to determine the approximate end point
of the reaction.
• Accurate titration is the subsequent titration
performed with the high accuracy when the end
point of the reaction has been already
established.
Number of titration Rough Accurate 1 Accurate 2 Accurate 3
Initial burette reading (cm3) 10.0 10.0 10.0 20.0
Final burette reading (cm3) 35.3 35.0 35.1 45.0
Titre (cm3), Vin - Vfin 25.3 25.0 + 25.1 + 24.9

3 =25.0 ml
 Observation
Volume of 1.0 Colour of
M NaOH (aq) indicator
When the two solutions just
added/ mL react and neither is in excess,
0 Colorless we have found the
5 Colorless equivalence point of the
10 Colorless titration.
15 Colorless
20 Colorless 𝟐𝟓
𝐧 𝑵𝒂𝑶𝑯 = × 𝟏 = 𝟎. 𝟎𝟐𝟓 𝒎𝒐𝒍𝒆𝒔
21 Colorless 𝟏𝟎𝟎𝟎
22 Colorless
23 Colorless 𝑵𝒂𝑶𝑯 𝒂𝒒 + 𝑯𝑪𝒍 𝒂𝒒 → 𝑵𝒂𝑪𝒍 𝒂𝒒 + 𝑯𝟐 𝑶(𝒍)
24 Colorless
25 Pink 𝒏 𝟎. 𝟎𝟐𝟓
26 Pink 𝑴 𝑯𝑪𝒍 = = = 𝟏 𝐦𝐨𝐥 𝒅𝒎−𝟑
𝑽 𝟎. 𝟎𝟐𝟓
27 Pink
28 Pink
 Observation
Volume of 1.0 Colour of WELL DONE!!!
M NaOH (aq) indicator
added/ mL
0 Colorless
5 Colorless
10 Colorless
15 Colorless Adding
20 Colorless dropwise!!

21 Colorless
22 Colorless OVERTITRATED!!!!!
23 Colorless
24 Colorless
25 Pink
26 Pink
27 Pink
28 Pink Adding by
stream!!
Acid-base titration

http://www.youtube.com/watch?v=8UiuE7Xx5l8&feature=related
 Standard solution

• Standard solution is a solution containing a

precisely known concentration of an element
or a substance.
• Standard solutions are usually prepared
from solid reagents.
• Standard solutions are used to determine
the concentrations of other substances, such
as analyte solutions in titrations.
 Back titration

• Back titration is useful if the endpoint of

the reverse titration is easier to identify
than the endpoint of the normal titration.

• Instead of titrating the analyte, a known

excess of standard reagent
(intermediate) is added to the solution,
and the excess is titrated.
 Back titrations are used when:
• one of the reactants is volatile, for
example ammonia.
• an acid or a base is an insoluble salt, for
example calcium carbonate
• a particular reaction is too slow
• direct titration would involve a weak acid
- weak base titration (the end-point of
this type of direct titration is very difficult
to observe)
 Example: Back Titration to Determine
the Amount of an Insoluble Salt
0.125g sample of chalk was placed in a 250mL beaker
and 50.00mL 0.200M HCl was added. The excess HCl
was then titrated with 0.250M NaOH. The average
NaOH titre was 32.12mL. Determine the mass of
calcium carbonate present in a chalk.
 Step 1: Determine the amount of HCl in excess from the
titration results
a) Write the equation for the titration:

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

acid + base → salt + water

b) Calculate the moles, n, of NaOH(aq) that reacted in the

titration:
n=MxV
M = 0.250 mol L-1
V = 32.12 mL = 32.12 x 10-3 L
n(NaOH(aq)) = 0.250 x 32.12 x 10-3 = 8.03 x 10-3 mol

c) From the balanced chemical equation, 1 mole NaOH reacts

with 1 mole of HCl. So, 8.03 x 10-3 mol NaOH reacted with 8.03 x
10-3 moles HCl. The amount of HCl that was added to the chalk
in excess was 8.03 x 10-3 mol.
Step 2: Determine the amount of calcium carbonate in chalk

a) Calculate the total moles of HCl originally added to the chalk:

n(HCl total added) = M x V
M = 0.200 mol L-1
V = 50.00 mL = 50.00 x 10-3 L
n(HCl total added) = 0.200 x 50.00 x 10-3 = 0.010 mol

b) Calculate the moles of HCl that reacted with the calcium

carbonate in the chalk.
n(HCl titrated) + n(HCl reacted with calcium carbonate) =
n(HCl total added)
n(HCl total added) = 0.010 mol
n(HCl titrated) = 8.03 x 10-3 mol
8.03 x 10-3 + n(HCl reacted with calcium carbonate) = 0.010
n(HCl reacted with calcium carbonate) = 0.010 - 8.03 x 10-3 =
1.97 x 10-3 mol
c) Write the balanced chemical equation for the reaction
between calcium carbonate in the chalk and the HCl(aq).

CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)

d) From the balanced chemical equation, calculate the moles of

CaCO3 that reacted with HCl.
From the equation, 1 mol CaCO3 reacts with 2 mol HCl so, 1
mol HCl reacts with ½ mol CaCO3. So, 1.97 x 10-3 mol HCl had
reacted with ½ x 1.97 x 10-3 = 9.85 x 10-4 mol CaCO3 in the
chalk.

e) Calculate the mass of calcium carbonate in the chalk.

n = mass / A
n = 9.85 x 10-4 mol (moles of CaCO3 that reacted with HCl)
MM(CaCO3) = 40.08 + 12.01 + (3 x 16.00) = 100.09 g mol-1
mass = n x A = 9.85 x 10-4 x 100.09 = 0.099g

The mass of calcium carbonate in the chalk was 0.099g.

 Reliability
Chemistry involves the interpretation of
quantitative measurements, usually made as a
part of experiment.
Each measurement has 4 aspects:
1) Object of measurement
2) Value
3) Units
4) Reliability
Example:
The mass of iron was 4.05 grams.
 Significant figures
• The accuracy of a measurement is indicated by
the number of digits used to represent it.
This digit has some uncertainty This digit has some uncertainty

These two digits are known for sure These three digits are known for sure

• Digits that result from a measurement such that

only the digit farthest to the right is not known
with certainty are called significant figures.
• The number of significant figures in a
measurement is equal to the number of digits
known for sure plus one that is estimated.
 When are zeros significant?
Rules for determining number of
Example:
significant figures:
• All nonzero digits are significant. 125.3
• Zeros between nonzero digits are 402
significant.
• In a number with no decimal point, zeros 33,000
at the end of the number (tracing zeros)
are not necessarily significant.
• If a number contains a decimal point,
zeros at the beginning (leading zeros) 0.00340
are not significant, but zeros at the end
of the number are significant.
 Why we need significant figures?
Significant figures express the accuracy of experiment.

+
33.100 mL Analytical pipette

20.256 mL
+
0.0005 mL
+
0.3 mL
rounding
53.6565 mL 53.7 mL
Measuring cylinder
 What to write in log book
Lab report template Complete lab report (long)

• Changes from • Risk assessment

procedure (if any) • Short intro
• Results • Procedure
• Observations • Results
• Calculations • Observations
• Calculations
• Short conclusion