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Urea: First Man-Made Organic

Compound

2014-15

UGEB 2370 Chap07

Organic Compounds in 19th C.

Believed to be produced only


by living organisms.

Exemplary materials include


sugar, starch, fats, urea (in
urine) etc.
Vitalism:
Vitalism:Organic
Organicchemicals
chemicalscould
could
be
bemodified
modifiedby
bychemistry
chemistrybut
butcould
could
only
onlybe
beproduced
producedthrough
throughthe
the
agency
agencyof
ofaa vital
vitalforce
force present
presentin
in
living
livingplants
plantsand
andanimals.
animals.

Only inorganic substances can be prepared in the lab,


but not organic compounds.
More liberal chemists: may be prepared in the lab, but
the starting materials must be organic matter.

2014-15

UGEB 2370 Chap07

The Stinky Student

1773: Urea was discovered in human urine.

F. Whler: High school expts. in the kitchen,


playing with salts & minerals. Occasionally,
tried evaporating urine (of dog, cat & his
own) to obtain beautiful white crystals
UREA.

2014-15

UGEB 2370 Chap07

Ammonium Cyanate vs. Urea?

1828: Trying simple exchange reaction between two


water-soluble salts. Any insoluble product(s) could then
be separated out of the reaction mixture.
AgOCN + NH4Cl

NH4OCN + AgCl

Silver
cyanate

Ammonium
chloride

Ammonium
cyanate

Silver
chloride

(soluble)

(soluble)

(soluble)

(insoluble)

Evaporation of liquid (7) gave white


crystals, which looked exactly like
the urea he had so often obtained
from dog and human urine!

[Ag+][OCN] +
[NH4+][Cl]

"I"Imust
must tell
tellyou
you that
that IIcan
canmake
makeurea
urea
without
withoutthe
theuse
useof
ofkidneys,
kidneys,either
eitherman
man
or
or dog.
dog. Ammonium
Ammonium cyanate
cyanateis
is urea."
urea."
2014-15

UGEB 2370 Chap07

Isomers?

Ammonium cyanate differs in physical & chemical


properties from urea.
Ammonium cyanate: ionic compound [NH4+][OCN-]
Urea: molecular compound:

Accurate measurements showed that both have the same


elemental composition, in the sense that the ratio of
different elements is the same, i.e., H:C:N:O = 4:1:2:1.
They are called ISOMERS (Latin iso identical; mero
part).

2014-15

UGEB 2370 Chap07

Covalent Bond & Molecules

Molecular compound: containing discrete units called


molecules. Within a molecule, non-metal atoms are
joined together by covalent bonds. Between molecules,
intermolecular forces exist to hold the molecules together.
Covalent bonding can be a complicated matter. What
introduced here is a simplified model which works for
most of the covalent substances.
Non-metal atoms tend to share electron(s) with another
one. The no. of electrons to be shared by some common
atoms in organic chemistry are:
H (1); O (2); N (3); C (4).
Less common atoms: F, Cl, Br, I (1)

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UGEB 2370 Chap07

Illustration of Covalent Bonding

Single bond:

Double bond:

Triple bond:

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UGEB 2370 Chap07

Molecular vs. Giant Covalent


Structure

Atoms can be connected one by one indefinitely to form a


giant covalent structure, e.g., diamond.
If the connections terminate somewhere and/or link to
each other, units with finite no. of atoms are formed and
they are called molecules, e.g., C60. The chemical
formula C60 indicates that each molecule contains 60
carbon atoms.
Most of the covalent substances are molecular.

2014-15

UGEB 2370 Chap07

Molecular vs. Giant Covalent


Structure
Alternating C-C
and C=C bonds.

In graphite: infinitely extending


layers are formed by regular
hexagons.

C60: regular hexagons mixed with


regular pentagons allow formation
of football shape molecule.

Single bonds
only.

Diamond
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UGEB 2370 Chap07

C60H60

Formula for molecules


Structural formula: showing the structure (how atoms are
bonded in one molecule), e.g.,

For clarity, single bonds connecting H are often omitted.


Sometimes, so are all single bonds.

Carbon skeleton formula: symbols H connected to carbon


and C are omitted.

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UGEB 2370 Chap07

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More Examples for Structural


Formula

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UGEB 2370 Chap07

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Intermolecular Forces
(1) Dipole-dipole force
If a bond connects two identical atoms, the bonding electrons
are equally shared between the two atoms, e.g., in H2.
If the two atoms are not identical, the bonding electrons are
not equally shared. They are more concentrated on atoms of:
N, O, F, Cl, Br, I than H, C, and hence partial charges develop
at the two atoms, e.g., in HCl and H3CCl.
These molecules are called polar molecules. The partial
charges result in an attractive force, dipole-dipole force,
between the molecules.

Dipole-dipole force holding two


molecules together.

Electron cloud is
shared equally.

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Electron cloud is more


concentrated on Cl atom.

UGEB 2370 Chap07

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Intermolecular Forces
(2) London force (studied by Fritz London)
At sufficiently low temperature, non-polar gases (e.g., H2, F2)
form liquids, in which the molecules are held by each other.
That means there are attractive forces between the non-polar
molecules of these gases. Fritz London recognized that the
motion of electrons in a molecule can create momentary
uneven distribution of charge, resulting in a momentary polar
molecule.

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Intermolecular Forces
(2) London force (contd)
Remarks:
(2a) London force exists for all molecules and atoms.

(2b) Molecules/
atoms with more
electrons have
larger London
force because the
electrons are held
less firmly and the
electron clouds
are more easily
distorted.

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Intermolecular Forces
(2) London force (contd)
Around us: boiling point of hydrocarbon CxHy
x ~ 1-4
x ~ 5-19
x ~ 20-25

Butane gas, C4H10.

2014-15

Gasoline

UGEB 2370 Chap07

Wax

15

Intermolecular Forces
(3) Hydrogen bonding
It is a special intermolecular force between a
F/O/N atom and a hydrogen atom bonded to
another F/O/N atom, e.g.,
Hydrogen bonding is significantly strong than
dipole-dipole force. In many cases, hydrogen
bonding is even
stronger than
London force of
large molecules.

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Molecular Compounds vs.


Ionic Compounds
Melting points:
Intermolecular forces
<< ionic bonds, covalent bonds, metallic bonds
Expected: ionic compounds have higher melting points than
molecular compounds.
NaCl (m.p. = 801 C, 28 e-)
NH4OCN (m.p. = 150 C, 32 e-)
Urea (m.p. = 133 C, 32 e-)
May be distinguishable by melting point measurement. (But
Whler didnt report anything about this.)
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Molecular Compounds vs. Ionic


Compounds
Electrical conducting property of aqueous solution:
If an ionic compound is soluble in water, the ions become
mobile and make the final solution electrical conducting.
If a molecular compound is soluble in water, the molecules
may or may not break down into mobile ions. For urea: the
molecules remain intact and neutral. Hence, the final solution
is NOT electrical conducting.
Pure water: not lit

Dissolving urea: not lit

Dissolving NaCl: lits

Apparently, Whler didnt do this kind of testing.


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Chemical Tests
After doing some chemical tests, Whler found that his product
behaved similarly to urea rather than NH 4OCN, and finally confirmed
that the product, obtained in glassware instead of living organisms,
was urea.
Importance: it was possible to produce organic compounds from
inorganic compounds by chemical means, instead of biological starting
materials and without relying on living organisms. The result
discredited vitalism, the theory that the chemicals of living organisms
are fundamentally different from those of inanimate matter. For this
discovery, Whler is considered by many the father of organic
chemistry.
Practical implication: organic compounds might then be produced in a
large-scale.

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Total Synthesis
Yet, for Whlers reaction, the starting materials might costly. Could
chemists go further to use cheap (or even free) starting materials to
obtain urea?
Total synthesis in organic chemistry: the complete chemical synthesis
of complex organic molecules from simpler pieces which are
commercially available in bulk quantities, and are often petrochemical
precursors, but sometimes bulk natural products (e.g. sucrose).
Industrial production of urea:
2NH3 + CO2
+ H 2O
NH3: from another well-known industrial process
CO2: from burning of hydrocarbons

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Total Synthesis
Further challenge: the variety of organic molecules relies on
the possibility of carbon chains, which contain different
numbers of C-C bonds and C-H bonds. Note that urea does
not contain these two types of bonds. The next challenge
would therefore be the creations of these two kinds of bonds.
This was achieved by Hermann Kolbe in 1845 on the total
synthesis of acetic acid.
Acetic acid:
containing C-C bonds and C-H bonds
Ancient production of acetic acid:
Sugar (e.g., in rice) ethanol (in wine) acetic acid
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Total Synthesis

Starting material:
carbon & FeS2 (both from mining)
Reagents: Cl2 & H2 (from electrolysis of NaCl solution)
Key steps:
C-C bond formation: decomposition by heating
C-H bond formation: replace Cl atoms with H atoms

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UGEB 2370 Chap07

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Melamine from Urea

Urea is also the starting material for melamine:


O

HH

HH
NN

NN
NN
HH

HH
NN

HH

NN
NN

6 NH3 3 CO 2

HH

Melamine is a precursor for the production


of scratch-resistant hard plastic.

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Kjeldahl Method

Kjeldahl Method: a chemical approach on protein content analysis

(1) Under vigorous condition: N in food NH3


(2) NH3 is then determined by a simple chemical method
In (1): All N in proteins & in melamine (and any other added stuff) is converted to NH 3. We cant tell which part is from proteins and which parts from added stuffs.

Due to its low cost & high nitrogen content per unit
mass, some dairy farmers cheat by adding melamine to
their milk products to fool the authoritys rather simple
check on protein content. It is also said that they
did so because they believed that melamine
could be converted to protein in the digestive
system of cows.

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The Accomplice in Crime

Cyanuric acid is a side product in melamine synthesis.

The geometry of cyanuric acid


enables it to make perfect
partnership with melamine thru
hydrogen bonding.

3 NH3
cyanuric acid

hydrogen bonds
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Fatal Network

At high concentrations and right pH, the 2 compounds


aggregate into huge insoluble 2-D networks.

The kidney enriches the 2 compounds & provides a slightly


alkaline environment for such process.

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The Martyrs (2007)

Infected cat kidney tissue


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Polarized light microscopy

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Practice on Bonding & Structure

There are a large number of isomers for the formula


CH4N2O. Work out one structural formula for each of the
follow skeletons (where
may be a single bond or
double bond):

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