Republic of the Philippines

CENTRAL BICOL STATE UNIVERSITY OF AGRICULTURE

San Jose, Pili, Camarines Sur 4418
Website: www.cbsua.edu.ph
Email Address: [email protected]
Trunkline: (054) 871-5531-33 local 101
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COLLEGE OF DEVELOPMENT EDUCATION

Learning Module in
WEEK
3 CHEM 102
Organic Chemistry

This learning module belongs to:

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(Name of Student)

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(Address)

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This learning module is prepared by:

LUDIVICO B. HOMILLANO, EdD

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 Republic of the Philippines
CENTRAL BICOL STATE UNIVERSITY OF AGRICULTURE
San Jose, Pili, Camarines Sur 4418
Website: www.cbsua.edu.ph
Email Address: [email protected]
Trunkline: (054) 871-5531-33 local 101
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WEEK Experimental Determination of

3 Organic Structures

LEARNING RESOURCES

1.0 ELEMENTAL ANALYSIS

1.1 QUALITATIVE ELEMENTAL ANALYSIS

To determine what elements are present in an organic compound, it is

necessary to decompose the compound so that the covalently bonded elements are
converted to water-soluble ions which can then be detected by qualitative inorganic
analysis. The simplest and most useful method for the decomposition of organic
compounds is sodium fusion.
The reaction is depicted in the equation below:
NaX
Na metal NaCN water soluble
Na2S ionic compounds
NaCNS
In organic form

1.2 QUANTITATIVE ELEMENTAL ANALYSIS

After determining which elements are present in a compound, one goes about
determining how much of each element is present - the % composition.
1.2.1 Carbon and Hydrogen

The amounts of carbon and hydrogen in an organic compound can be measured by

combustion of a weighed sample in a stream of oxygen in an apparatus called a
combustion train (see Figure 2.1).

heat
quantitative C, H + CuO Cu + C02 + H2O
combustion

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 Republic of the Philippines
CENTRAL BICOL STATE UNIVERSITY OF AGRICULTURE
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Website: www.cbsua.edu.ph
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Trunkline: (054) 871-5531-33 local 101
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All of the carbons in the organic compound combine with oxygen to form carbon
dioxide, while all of the hydrogens combine with oxygen to form water.

Figure 2.1 Schematic representation of a combustion train for the quantitative

determination of C and H
The resulting water and carbon dioxide are absorbed in tubes that contain
magnesium perchlorate and soda lime, respectively. The tubes are then weighed in
order to determine the amounts of water and carbon dioxide produced from
combustion of the weighed sample. From these measurements, the masses and
percentages of carbon and hydrogen in the sample can be calculated as follows:

atomic wt C
weight of C in the sample = wt. C02 x
molecular wt CO2

weight of C
mass and % C in the sample = x 100
percentage of C weight of sample

2 x atomic wt H
weight of H in the sample = wt. H20 x
molecular wt H2O
weight of H
mass and % H in the sample = x 100
percentage of H weight of sample

The quantitative determination of other elements is accomplished by using

methods which make use of the same principle as above, i.e., to transform an
element to a compound whose amount can easily be measured.

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 Republic of the Philippines
CENTRAL BICOL STATE UNIVERSITY OF AGRICULTURE
San Jose, Pili, Camarines Sur 4418
Website: www.cbsua.edu.ph
Email Address: [email protected]
Trunkline: (054) 871-5531-33 local 101
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1.2.2 Halogens, Sulfur and Nitrogen

The halogens (X) are quantitatively determined by the Carius method (using
hot fuming nitric acid, HN03) or the Parr method (using sodium peroxide, Na2O2).

HNO3 Ag+
X X- AgX
Na2O2
The amount and percentage of halogen are calculated as follows:

weight of X in the sample = wt. AgX x atomic wt X

mass and percentage of formula wt AgX

wt of X
halogen % X in the sample = x 100
wt of sample

Sulfur is also determined by the Carius or Parr method.

The amount and percentage of sulfur are calculated as follows:

atomic wt S
weight of S in the sample = wt. BaSO4 x
formula wt BaS04
mass and percentage of
wt of S
% S in the sample = x 100
wt of sample

Nitrogen is determined by the Dumas method. In this procedure, the nitrogen

present in the organic sample is transformed to nitrogen gas and its volume
measured.
oxidization reduction
N Oxide of N N2 gas

To calculate the amount of nitrogen (N 2) the gas law is used:

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Website: www.cbsua.edu.ph
Email Address: [email protected]
Trunkline: (054) 871-5531-33 local 101
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PV = nRT

The amount and percentage of nitrogen in the sample are calculated as follows:
2 x atomic wt N
weight of N in the sample = wt. N2 x
Mass and percentage molecular wt N2
of nitrogen
wt of N
% N in the sample = x 100
wt of Sample

1.23 Oxygen

There is no direct way of determining the % of oxygen. The amount of O is

determined indirectly by difference. If the sum of the percentages of the elements is
not 100 %, the difference is due to oxygen.

2.0 EMPIRICAL AND MOLECULAR FORMULA DETERMINATION

The empirical formula expresses the relative number (not the actual number)
of the different atoms present in a molecule. It can easily be calculated from the %
composition. Some examples of empirical formulas are the following:

CH CH2 CH2O C3H7N

Note that the numbers of atoms are in the simplest whole number ratio.

CH 1:1
CH2 1:2:1
CH2O 1:2
C3H7N 3:7:1

The molecular formula, which expresses the actual number of each kind of
atom present, can be derived from the empirical formula. The molecular formula is a
whole number multiple of the empirical formula. In some cases, the molecular formula

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is the same as the empirical formula. The compounds with molecular formulas C2H4,
C3H6, C4H8 all have the empirical formula CH2.

In order to derive a molecular formula from an empirical formula, the molecular

weight (molecular mass) of the compound being analyzed must first be known.

There are several ways of determining molecular weight. For gaseous organic
compounds and liquid substances of moderate volatility, molecular weights may be
determined by vapor density experiments. The molecular weight of high-boiling
liquids and nonvolatile solids can be determined by measurements of freezing-point
depression or boiling-point elevation. Highly accurate molecular weights are
determined by mass spectrometry.

The following example illustrates how calculations for % composition,

empirical and molecular formulas can be carried out from elemental analysis data.

EXAMPLE 2-1.

An 8.00 mg sample of an organic compound was subjected to quantitative

combustion to give 15.33 mg of carbon dioxide and 9.36 mg of water. The molecular
weight was found to be 46. Calculate the % composition, empirical and molecular
formulas of the organic compound.
Given: 15.33 mg C02 and 9.36 mg H20 from combustion of 8.00 mg
of organic compound
Asked for: 1) % composition
2) empirical formula
3) molecular formula
Solution:
Step 1: Calculate % composition
12

• weight C in sample = 15.33 mg x

44

%C= x 100 = 52.25 %

8 mg
2
• weight H in sample = 9.36 mg x = 1.04 mg
18

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1.04 mg
%H = x 100 = 13.00%
8.00 mg

• the analysis does not show the presence of other elements

• % C + % H = 52.25% + 13.00% = 65.25%
• % O = 100% - 65.25% = 34.75%

Step 2: Calculate the number of moles of each element present.

To simplify calculations, consider 100 g of the compound. This contains 52.2 g

C, 13.0 g H and 34.8 g O.
• moles C = 52.25 g = 4.35 moles
12 g/ mol
• moles H = 13.00 g = 13.00 moles
1.0 g/mol

• moles O = 34.8 g = 2.18 moles

16 g/mol

Step 3: Get the of moles of the elements to derive the empirical formula (EF)

•sincea mole of an element contains the same number of atoms as a mole

of any other element, the relative number of C, H, and O atoms in the
organic compound is the ratio of moles.
ratio of moles: C 4.35 H 13.0 O 2.18

•reduce to smallest whole numbers by dividing the number of moles of each

element by the smallest number (least common denominator)

C 4.35 H 13.0 O 2.18 C2H6O

2.18 2.18 2.18 empirical formula

Step 4: Derive the molecular formula (MF) from the empirical formula

MW (molecular wt)
=n factor by which the EF should
EFW (weight from EF) be multiplied to get MF

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 Republic of the Philippines
CENTRAL BICOL STATE UNIVERSITY OF AGRICULTURE
San Jose, Pili, Camarines Sur 4418
Website: www.cbsua.edu.ph
Email Address: [email protected]
Trunkline: (054) 871-5531-33 local 101
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46

46

.1 C2H6O
molecular formula

This is an example of an organic compound whose molecular formula is the

same as its empirical formula.

3.0 DERIVATION OF STRUCTURAL FORMULAS FROM A MOLECULAR

FORMULA

From the molecular formula, the next step is to derive possible structural
formulas. A structural formula tells us how the atoms in a molecule are bonded to
each other. Oftentimes for a given molecular formula there are several ways of
bonding the atoms to one another.

Let us work out the following problems.

EXAMPLE 2-2

Propose possible structural formulas for each of the following molecular formulas:
a) C2H6O; b) C3H6O

For a molecular formula, we should calculate for the value of p so that we will
know the total number of rings and/or double and triple bonds (degree of
unsaturation) that may be present in the structural formulas.

2+2C–H+N-X
p= 2 = number of rings and/or double or triple bonds

in the formula for p:

C refers to number of carbon atoms
N refers to the number of nitrogen atoms
H refers to number of hydrogen atoms
X refers to number of halogen atoms

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 Republic of the Philippines
CENTRAL BICOL STATE UNIVERSITY OF AGRICULTURE
San Jose, Pili, Camarines Sur 4418
Website: www.cbsua.edu.ph
Email Address: [email protected]
Trunkline: (054) 871-5531-33 local 101
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Note:
for 1 ring, p = 1
for 1 double bond, p = 1
for 1 triple bond, p = 2

a). C2H6O
2+2 (2) -6 =0 no rings, double bonds or triple bonds
p= 2

You have learned previously that H forms I covalent bond, carbon forms 4
covalent bonds and oxygen forms 2 covalent bonds in uncharged or neutral
molecules.

There are only two ways of connecting or linking the two carbon atoms, six
hydrogen atoms and one oxygen atom to each other by means of single bonds.

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 Republic of the Philippines
CENTRAL BICOL STATE UNIVERSITY OF AGRICULTURE
San Jose, Pili, Camarines Sur 4418
Website: www.cbsua.edu.ph
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Trunkline: (054) 871-5531-33 local 101
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NOTE: There are other possible structural formulas but they do not correspond to
stable molecules.

If there are several possible structural formulas from a molecular formula, which one
is the actual structure of the unknown compound? This question can be answered by
a careful consideration of the chemical and physical properties of the compound. The
modern chemist makes use of spectroscopic techniques: nuclear magnetic
resonance (NMR) spectroscopy, infrared (IR) spectrophotometry, ultraviolet (UV)
spectrophotometry and mass spectrometry (MS). The discussion of these techniques
is beyond the scope of our organic chemistry course.

EXPLORE
(Optional for the students using the hard copy)

You may visit these link/s:

https://www.youtube.com/results?search_query=Quantitative+a
nalysis+of+organic+compounds
https://www.youtube.com/watch?v=O8kqpqk6cAE

REFERENCES

Ball, P. (1994). Designing the Molecular World. New Jersey: Princeton University
Press
Brock, W. H. (1993). The Norton History of Chemistry. New York: W.W. Norton and
Co.
Brown, W. H. (1982). Introduction to Organic Chemistry (3rd Edition). Boston: Wilier
Grant Press
Carey, F. A. (1992). Organic Chemistry (2nd Edition) New York: Mc Graw-Hill, Inc.

Page 10 of 11
 Republic of the Philippines
CENTRAL BICOL STATE UNIVERSITY OF AGRICULTURE
San Jose, Pili, Camarines Sur 4418
Website: www.cbsua.edu.ph
Email Address: [email protected]
Trunkline: (054) 871-5531-33 local 101
ISO CERTIFIED

McMurry, J. (1992). Organic Chemistry (3rd Edition) California: Brooks/Cole

Publishing Co.
Morrison, R. T. & Boyd, R. N. (1989) Organic Chemistry (5th Edition), Boston: Allyn
and Bacon
Solomons, T.W.G. (1994) Fundamentals of Organic Chemistry (4th Edition). New
York: John Wiley and Sons, Inc.

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