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Chapter 1: Chemical Bonding
Chapter 2: Alkanes
Chapter 3: Conformational Analysis of Alkanes and Cycloalkanes
Chapter 4: Alcohols and Alkyl Halides
Chapter 5: Structure and Preparation of Alkenes. Elimination Reactions
Chapter 6: Reactions of Alkenes. Addition Reactions
Chapter 7: Stereochemistry
Chapter 8: Nucleophilic Substitution
Chapter 9: Alkynes
Chapter 10: Conjugation in Alkadienes and Allylic Systems
Chapter 11: Arenes and Aromaticity
Chapter 12: Reactions of Arenes: Electrophilic Aromatic Substitution
Chapter 13: Spectroscopy
Chapter 14: Organometallic Compounds
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Summary:
Understanding the structure and bonding of organic molecules is fundamental to being able to
understand their properties and reactions. This is because the properties and reactions are controlled
by the interactions between molecules which are in turn dictated by the types of bonds within those
molecules.
Although you may feel that most of this chapter is review from your General Chemistry course(s),
many students are not as strong as they need to be to survive the adventure that lies ahead, so make
sure you start your organic course in good shape.
As you will see later, understanding the location of electrons is especially important as it is the
arrangement of the electrons that creates the bonds between the atoms, and chemical reactions are
just a reorganisation of those electrons to form new bonds.
Hybridisation
Atoms:
All matter is composed of atoms. Atoms are a collection of various subatomic particles.
You should be familiar with the subatomic particles how to determine how many of each a
specific atom has and what the atomic mass of an atom represents. Try some questions. If you
are not comfortable perhaps you need to look a bit more in depth.
In organic chemistry, as far as the compounds are concerned, the atoms of greatest interest are
located the first three rows of the periodic table. Later when one probes deeper into synthetic
methods, one needs to be familiar with some of the heavier metals as well.
probability in 3D space, about a nucleus, where an electron may be found. In organic chemistry
one needs to be most familiar with the s- and p-type orbitals. These orbitals can be described by
using quantum numbers. The orbitals for the electrons in carbon, and the associated quantum
numbers are given below. The nucleus of the carbon atom would reside at the centre of the x,y,z
coordinate.
You should be familiar with the meaning of quantum numbers, how to name an orbital using
quantum numbers or what orbital a set of quantum numbers defines. Try some questions. If your
struggling you'll need to review the meaning of quantum numbers.
The electron configuration of an atom describes the number of electrons that atom possesses and
the orbitals in which those electrons are to be found.
e.g. electron configurations of carbon
simple
short form
[He]2s2 2p2
You should be familiar with how to determine an electron configuration for an atom and identify
the valence electrons. You should be able to identify both ground and excited state electron
configurations. Try some questions. If you are having trouble you should review how to
determine electron configurations.
Bond types:
Why is it important to understand the structural arrangement of electrons in an atom?
In everyday life, chemistry arises out of the interaction of molecules with molecules... but what is a
molecule? It is a collection of atoms. When the atoms come together their electron clouds interact
with one another and if this interaction is 'favourable' then bonding occurs.
One of the driving forces behind bonding is an atoms desire to obtain a stable valence electron
configuration. For the atoms that are most important in organic chemistry, (N, C, O, Cl, Br, and I),
this is an octet of electrons, which is similiar to the valence electron configuration of the nearest
noble gas (ns2np6).
Ionic
bonds
result
when
electrons
are
tranfered
between
Covalent bonds result when valence electrons are shared between atoms.
atoms.
You should be able to identify whether an ionic or covalent bond is being formed between atoms.
Try some questions. If you are having difficulty then you need to review bonding.
Most bonds within organic molecules will be covalent. The execeptions will be compounds which
possess metal atoms (where the metal atoms should be treated as ions). It is important to note that
the electron distribution within a covalent bond is not always symmetrical. If it is not then the bond
is said to be polar as opposed to non-polar.
If a bond is covalent you should be able to identify whether it is polar or non-polar. Try some
questions. If you are having difficulty then you need to review bond polarity.
Lewis Diagrams:
Lewis Diagrams give the connectivity between atoms in a molecule; they tell you nothing about
the arrangement of the atoms of a molecule within 3D space (that is left to VSEPR or
Hybridisation).
You should be able to draw a Lewis diagram for both organic and inorganic molecules as the
latter are often used as reagents in organic syntheses. Examples. If you are not yet comfortable
with detemining a Lewis diagram, take a look at an outline of how to determine a Lewis diagram.
In reality, electrons in a molecule are being delocalized within that molecule. Consequently, more
than one Lewis diagram can be used to describe molecules which possess multiple bonds.
Collectively these Lewis diagrams are then known as resonance structures and their sum is often
represented as the resonance hybrid (note a resonance hybrid is not a Lewis diagram!).
You should be able to draw all reasonable resonance structures for a given organic molecule.
Examples. If you are not yet comfortable with examining the resonance in a molecule you should
Shapes of Molecules:
In order to view some of the structures for this section, you will need the web "plug-in", "CHIME".
If you do not have it already installed, you should be able to download it for free from the linked
Website. CHIME is a browser that allows you to visualise and manipulate molecules as 3D
structures. Check here if you don't know how to use Chime.
When determining the shape of a molecule the premise is that groups of electrons surrounding an
atom are repelled as far as possible from each other to minimize the overall energy of the molecule.
Groups of electrons can refer to electrons that participate in bonding (single, double, or triple) or to
those that are non-bonding (e.g. lone pair electrons). The number and types of groups are
determined from a Lewis diagram.
Not only is it important for a chemist to be able to visualize a structure, they must also be able to
effectively (clearly!) transfer this knowledge onto a piece of paper!!!!!!
A molecule is visualized as if it were centered in the plane of the paper and, generally, so that the
most number of atoms possible are in that plane. Unbroken lines are used to represent bonds in the
plane of the paper, hashed wedges represent bonds going back out of the plane of paper and solid
wedges represent bonds coming out of the plane of the paper.
There may be several different ways that you can represent a molecule on a piece of paper. You
should be able to discriminate which of those drawings most clearly represent the structure of a
molecule.
You should be able to determine the shape of a molecule by looking at the electronic and
molecular geometry about all non-terminal atoms. In doing so you must be able to present clear
drawings of your conclusions. Try some questions. If you are having problems doing this you will
need to review VSEPR.
Once the shape of a molecule is known, by referring to the sum of the bond polarities, the
molecular polarity can be determined. This is important when examining the reactivity of a
molecule.
You should be able to indicate a molecule's polarity.
Hybridisation:
Covalent bonds are formed when atomic orbitals overlap. There are two types of orbital overlap
that an organic chemist needs to be familiar with. Sigma, , overlap occurs when there is one
bonding interaction that results from the overlap of two orbitals. Pi, , overlap occurs when two
bonding interactions result from the overlap of orbitals.
The organic chemist also needs to realise how these orbital overlaps relate to the type of bonding
that is occuring between atoms:
single bond
overlap
double bond and overlaps
triple bond
and two overlaps
If one tries to correlate the overlap of atomic orbitals to the shape of a molecule, however, the
expected geometry does not correspond to a maximum orbital overlap. Take a look at methane,
CH4. VSEPR predicts a tetrahedral geometry about the carbon atom but this is not achieved when
one considers a maximum orbital overlap between four 1s orbitals of H and the 2s, 2p x, 2py and 2pz
orbitals of carbon.
Hybridisation is a solution to this problem. It is the imaginary mixing of the 2s, 2px, 2py and 2pz
atomic orbitals of carbon to form a new set of 'hybrid' orbitals that orient themselves in the
desired VSEPR geometry. The hybrid orbitals are equivalent to one another making all orbital
overlaps equivalent, therefore, all C-H bonding interactions equivalent.
Hybrid orbitals are named by considering the type and number of atomic orbitals from which they
arose. For CH4 then the hybridisation for the carbon is sp3. One sees that the hybridisation of an
atom can be determined very quickly by considering the number of electron groups about an
atom. Hybrid orbitals are responsible for all the bonding overlaps in a molecule.Unhybridised
orbitals are responsible for all the bonding overlaps in a molecule
.
You should be able to predict the hybridisation of all non-hydrogen and non-terminal atoms in a
molecule and draw the bonding interactions in that molecule based on the hybridisation model.
Try some questions.
If you are still having difficulty with hybridisation, then you will need to review your concept of
hybridisation.
Chapter 2 : Alkanes
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Summary:
With the basis of structure and bonding behind us, we are ready to begin examining the structure,
reaction and applications of organic compounds, and this start with the simplest organic systems,
the alkanes.
As you head into all the material ahead, it is important the remember that in almost all of the
reactions that you will encounter, the reactions occur directly at or adjacent to the functional
groups within the molecule.
The physical properties of molecules such as melting points, boiling points and solubility are
dictated by intermolecular forces.
Functional Groups
Hydrocarbons
Types of hydrocarbons ?
Alkanes
Nomenclature
Physical Properties
Structure
Isomers
Stability
Reactivity
Sample questions
Cycloalkanes
Nomenclature
Physical Properties
Structure
Reactivity
Heat of Combustion
Drill Problems
Chapter 2 : Alkanes
Functional Groups
As organic chemistry unfolds, take notice that the reactions occur directly at or immediately
adjacent to the functional groups, and that recognising the functional groups is the key to
recognising the type of reaction.
What is a reaction ?
A reaction is the process by which one compound is transformed into a new compound.
Chapter 2 : Alkanes
Alkane
Alkene
Alkyne
Arene
Alcohol
Alkyl halide
Amine
Epoxide
Ether
Nitrile
Nitroalkane
Thiol
Aldehyde
Ketone
Carboxylic Acid
Acyl halide
Acid anhydride
Ester
Amide
Chapter 2 : Alkanes
Functional
Group
Questions
C1
C8
C12
C14
C17
C19
Answers ?
Chapter 2 : Alkanes
Hydrocarbons
Hydrocarbons are compounds that only contain H and C atoms, but they can be subdivided
according to the following tree diagram depending on the bond types that are present.
Hydrocarbons
CcHh
Alkanes
Alkenes
Alkynes
Arenes
Only CC bonds
CC and bonds
C=C
CC and 2bonds
CC
6 C cyclic array
all C sp2 hybridised
Chapter 2 : Alkanes
Alkanes:
Simplest organic molecules with only C and H atoms. Commercially important as fuels and oils.
Nomenclature:
Functional group suffix = -ane (review)
Functional group prefix = alkylPhysical Properties:
The low polarity of all the bonds n alkanes means that the only intermolecular forces between
molecules of alkanes are the very weak induced dipole - induced dipole forces, which are easily
overcome. As a result, compared to other functional groups, alkanes tend to have low melting and
boiling points and very low solubility in polar solvents such as water (remember "oil and water
don't
mix"
and
the
adage
"like
dissolves
like").
Structure:
Alkanes are the simplest organic compounds, comprised of only sp 3 hybridised C and H atoms
connected by bonds.
They have a generic formula of C nH2n+2 (a relationship that also defines the maximum number of
hydrogen atoms that can be present for a given number of C atoms).
Structures of the simple C1 to C4 alkanes are shown below in a variety of representations. As the
number of C atoms increases then other isomeric structures are possible
Methane
CH4
(b.pt. = -160oC)
Ethane
C2H6
(b.pt. = -89oC)
Propane
C3H8
(b.pt. = -42oC)
Butane
C4H10
(b.pt. = -0.4oC)
Stability:
More branched alkanes are more stable that linear alkanes, e.g. 2-methylpropane is more
stable than n-butane.
Reactivity:
Since C and H atoms have very similar electronegativities, so all the bonds in alkanes (C-C
Chapter 2 : Alkanes
Isomeric Alkanes
The molecular formulae for the C1 to C3 alkanes lead to single, unique structures.
However for C4H10, there are two possible constitutional isomers. It is important to be able to
recognise isomers because there can have different chemical, physical properties and biological
properties. The constitutional isomers of C4H10 are shown below along with some properties:
m.pt.=
-139oC
b.pt. = -0.4oC
Hf = -125.6 kJ/mol
n-butane
(-30.0 kcal/mol)
Hc = -2877 kJ/mol
(-687 kcal/mol)
m.pt.=
-161oC
b.pt. = -10.2oC
Hf = -135.6 kJ/mol
isobutane
(-32.4 kcal/mol)
Hc =-2868 kJ/mol
(-685 kcal/mol)
n-pentane
b.pt. = 36.1 oC
Hf = -147 kJ/mol
(-35.1 kcal/mol)
Hc = - 3509 kJ/mol
(- 839 kcal/mol)
b.pt. =
30 oC
Hf = -154.1 kJ/mol
isopentane
(-36.8 kcal/mol)
Hc = -3502 kJ/mol
(-837 kcal/mol)
b.pt. =
9.5 oC
Hf = -168.0 kJ/mol
neopentane
(-40.1 kcal/mol)
Hc = -3493 kJ/mol
(- 835 kcal/mol)
Chapter 2 : Alkanes
Cycloalkanes
Another type of molecule containing only sp3 hybridised C and H atoms connected by bonds is
possible with a ring of 3 or more C atoms. These are the cycloalkanes which are fairly common in
the world of organic chemistry, both man-made and natural.
Nomenclature:
Functional group prefix = cyclo- (review)
Physical Properties:
Like alkanes, the low polarity of all the bonds in cycloalkanes means that the only intermolecular
forces between molecules of cycloalkanes are the very weak induced dipole - induced dipole forces,
also known as van der Waals forces which are easily overcome. As a result, compared to other
functional groups, but like alkanes, cycloakanes tend to have low melting and boiling points.
Structure:
They have a generic formula of CnH2n, (note: there 2 less H atoms compared to the analogous
alkane).
The C3 to C6 cycloalkanes
Cyclopropane
C3H6
Cyclobutane
C4H8
Cyclopentane
C5H10
Cyclohexane
C6H12
Reactivity:
Very similar reactivity to the closely related alkanes which have the same types of bonds.
Since C and H atoms have very similar electronegativities, both the C-H and C-C bonds are
non-polar.
As a result, cycloalkanes, like alkanes, are not a very reactive functional group
Name
C3H6
cyclopropane
C4H8
cyclobutane
C5H10
cyclopentane
C6H12
cyclohexane
Line Diagram
Molecular Model
Substitution on the ring is also possible. When the ring is larger than the longest continuous chain of
carbon atoms in a substituent, the ring will be the parent compound.
Example
1.)
The ring is larger than the ethyl group so the name is:
ethylcyclopentane
NOTE:
no
number
is
needed
as
there
is
only
single
substituent.
Example
2.)
3.)
The
NOTE:
name
is:
4-isopropyl-1,2-dimethylcyclohexane
this gives to lowest total number for the three substituents, i.e. the shortest distance
When the chain is longer than the ring, the ring becomes a substituent on the chain. As a substituent,
the ring is named following the rules for alkanes, drop the -ane and replace it with -yl. For example
a cyclopropane ring as a substituent becomes a cyclopropyl group.
Example
4.)
4-cyclobutyl-5-cyclopropyl-2-methylheptane
Useful Concepts
redox reactions.
Organic chemists will normally describe a reaction as either oxidation or reduction
Add the total for atoms attached to the C in question, then switch the sign.
Here are a few examples, and a couple of schemes that show important relationships:
Tips: In General Chemistry or High School you may have learnt that O is always -2, however it is
better to count each bond to an O as -1 since there is a difference between C=O and C-O as seen by
comparing the aldehyde and the alcohol in the diagram above. After all , the -2 statement is
wrong.... for example in oxygen gas, the oxidation state is zero
Chapter 3:
Conformations of Alkanes and Cycloalkanes
<>
Summary:
The different spatial arrangments that a molecule can adopt due to rotation about sigma bonds are
called conformations
and
hence
conformational
isomers
or conformers.
The study of the energy changes that occur during these rotations is called conformational
analysis.
This is important because the structure of a molecule can have a significant influence on the
molecular properties, including dictating the outcome of a reaction. Although the ideas are
developed for the simplest functional groups, the alkanes, the same principles can be expanded and
applied to other functional groups.
Conformational analysis has its own language. A list of the key terms is provided with direct links
to explanations.
The ability to draw and interpret the different diagrams (wedge-dash, sawhorse, Newman) used to
represent the different conformations is also important.
Drill Problems
Chapter 3:
Conformations of Alkanes and Cycloalkanes
Conformational Language
An alphabetical list of key terms in the language of conformational analysis is provided below,
linked
to
the
more
detailed
descriptions
within
the
chapter
pages
Anti
Eclipsed
Staggered
Gauche
Syn
Conformations
Conformers
Rotamers
Heteroatom
Heterocycle
Puckered
Ring flipping
Axial
Equatorial
Chair
The
most
cyclohexane.
Boat
Strain
Angle strain
Steric strain
stable
conformation
for
Torsional angle
Angle between C-X and C-Y bonds in a X-CC-Y system. Also known as a dihedral angle.
Ring strain
Chapter 3:
Conformations of Alkanes and Cycloalkanes
wedge-dash
sawhorse
Newman
cyclohexane
Wedge-dash
diagrams:
Usually drawn with two bonds in the plane of the page, one infront, and one behind to give the
molecule perspective. When drawing wedge-dash it is a good idea to visualise the tetrahedral
arrangement of the groups and try to make the diagram "fit" this. As a suggestion, they seem to be
most effective when the "similar" pairs of bonds (2-in-plane, 2-out-of-plane) are next to each other,
see below:
Sawhorse:
Sawhorse diagrams are similar to wedge-dash diagrams, but without trying to use "shading" to
denote the perspective. The representation to the right of propane has been drawn so that we are
looking at the molecule which is below us and to our left.
Newman:
These projections are drawn by looking directly along a particular bond in the system (here a C-C
bond) and arranging the substituents symmetrically around the atoms at each end of that bond. The
protocol requires that the atoms within the central bond are defined as shown below:
In order to draw a Newman projection from a wedge-dash diagram, it is useful to imagine putting
your "eye" in line with the central bond in order to look along it. Let's work through an example,
consider drawing a Newman projection by looking at the following wedge-dash diagram from the
left hand side.
First draw the dot and circle to represent the front and back C respectively
Since the front carbon atom has an H atom in the plane of the page pointing up we can add
that first
The back carbon atom has an H atom in the plane of the page pointing down
Now add the other bonds to each C so that it is symmetrical
The groups / bonds (blue) that were forward of the plane of the page in the original wedge-
Try the same thing, but looking from the right to generate the other Newman projection
Cyclohexane
Drawing cyclohexane so that it looks like a chair can be the key to appreciating the axial and
equatorial positions....
First step is drawing the chair itself. Although the chair "looks better" when slightly angled, it
maybe easier to "learn" to draw it with the middle protion horizontal.
Chapter 3:
Conformations of Alkanes and Cycloalkanes
Alkanes
By starting with simple alkanes we can prepare ourselves for the more complex world that lies
beyond.....
Methane:
CH4
Ethane:
CH3-CH3
STAGGERED
Look at how the each H-C-H bond angle is bisected by a C-H bond on the
adjacent C atom. This is the most stable conformation for ethane since the
torsional strain is minimised.
ECLIPSED
Think like an astronomer....each of the C-H bonds is aligned with a C-H
bond on the adjacent C atom so that the H attached to the front C obscures
(eclipses) those on the rear C
Propane:
CH3-CH2-CH3
Chapter 3:
Conformations of Alkanes and Cycloalkanes
Higher Alkanes
The same basic ideas of conformational analysis developed for simple alkanes also apply, but some
new situations are encountered.
Butane:
CH3-CH2-CH2-CH3
ANTI
a staggered conformation with the Me
groups at 180o with respect to each other
GAUCHE
a staggered conformation with the Me
groups at 60o with respect to each other
SYN
an eclipsed conformation with the Me
groups at 0o with respect to each other
GAUCHE
a staggered conformation with the Me
groups at 60o with respect to each other
(note: the two gauche conformations are not quite the same, try to convince yourself of this. How
are they related ?)
Chapter 3:
Conformations of Alkanes and Cycloalkanes
Cycloalkanes
Commonly encountered in natural products, such as steroids. Cyclopentanes and cyclohexanes are
the most common. Other than cyclopropane these are non-planar or "puckered" systems. This
puckering relieves some of the ring strain by lowering angle and torsional strains.
Cyclohexane:
C6H12
The most stable conformation of cyclohexane is the chair form shown to the right. The C-C-C
bonds are very close to 109.5o, so it is almost free of angle strain. It is also a staggered
conformation and so is free of torsional strain. You can rotate the molecule in the image to show
this just like a Newman projection.
The chair is the most stable conformation of cyclohexane.
A second, much less stable conformer is the boat conformation. This too is almost free of angle
strain, but in contrast has torsional strain associated with eclipsed bonds at four of the C atoms. You
can rotate the molecule in the image to show this just like a Newman projection.
In addition, a steric interaction of the H atoms inside the bow and the stern, known as the flagpole
interaction also destabilises the boat.
Click here to highlight flagpole hydrogen atoms
Click here to reset colors
A third conformation is produced by twisting the boat to give the twist or skew-boat conformation.
The twist relieves some of the torsional strain of the boat and moves the flagpole H further apart
reducing the steric strain. Consequently the twist boat is slightly more stable than the boat.
Click here to highlight flagpole hydrogen atoms
Click here to reset colors
Conformational rotation (also known as ring-flipping) of cyclohexane interconverts two chair
forms. This proceeds from chair to twist boat to boat to twist boat to chair. Watch the animation
carefully.
Chair Cyclohexane
In chair cyclohexane there are two types of positions, axial and equatorial. The axial positions
point perpendicular to the plane of the ring, whereas the equatorial positions are around the plane
of
the
ring.
These
can
be
highlighted
in
the
diagram
below.
OTHER CYCLOALKANES
Other than cyclopropane (which must be planar), cycloalkanes are also "puckered" to relieve some
of the ring strain. The structures of some of the smaller cycloalkanes are shown below with the
planar structures for contrast. In each case, manipulate the images to look for the deviation from
planarity and the effect this has on the eclipsing interactions of adjacent H atoms and C-C bonds. In
order to be able to compare the strain in each member of the cycloalkane series, the heat of
combustion per methylene (i.e. -CH2-) is also given.
C3H6
CYCLOPROPANE
Hc / CH2 = 166.6 kcal/mol
C4H8
CYCLOBUTANE
Hc / CH2 = 162.7 kcal/mol
planar most stable structure
C5H10
CYCLOPENTANE
Hc / CH2 = 157.3 kcal/mol
planar most stable structure
C6H12
CYCLOHEXANE
Hc / CH2 = 156.1 kcal/mol
planar most stable structure
Chapter 3:
Conformations of Alkanes and Cycloalkanes
Substituted Cyclohexanes
Substituents on cyclohexane can, in principle, occupy either axial or equatorial positions. However,
in general, equatorial substituents are more preferred since they are more stable because of reduced
steric interactions.
This
is
shown
in
the
following
example
for
methycyclohexane.
In the equatorial system, the methyl group is anti to the C-C bonds in the rest of the ring system.
However, in the axial conformation, a steric interaction of the methyl group with the two axial
hydrogen atoms on the same face of the ring destabilises the axial conformation. In the images
below, this 1,3-diaxial interaction can be highlighted and contrasted with the equatorial conformer.
The effect is most obvious when viewed in the spacefilling model.
EQUATORIAL
AXIAL</B< CENTER>
The larger the alkyl substituent is, the greater the preference for the equatorial position since the
larger the group the greater the steric interaction with the axial hydrogens.
Chapter 3:
Conformations of Alkanes and Cycloalkanes
Polycyclic Systems
Both nature and mankind has created many examples of compounds that contain more than one
ring system. These can be classified depending on how many rings are present and how the rings
are joined together.
If there is a single carbon atom common to two rings, then the
system is said to be "spirocyclic" and the carbon can be described
as the "spirocenter". The simplest example is spiropentane.
If two or more atoms are shared between more than one ring then
the system is said to be "polycyclic" in general terms or as
bicyclic, tricyclic, tetracyclic etc. depending on how many rings
systems are present. The simplest polycyclic system is
bicyclobutane.
When there are two common atoms in the rings, then it is a
"fused" system, as in bicyclobutane.
If there are more than two common atoms then the a "bridged"
system
is
obtained,
the
simplest
example
being
bicyclo[1.1.1]pentane.
Some interesting examples are provided below. See if you can recognise which class they would
belong to.
Cubane
Adamantane
Chapter 3:
Conformations of Alkanes and Cycloalkanes
Heterocycles
Of course atoms other than C can occur as part of the cyclic structure. Such atoms, which are
known as heteroatoms, e.g. N, O, S give rise to heterocycles. These heterocycles are, in general,
very similar to the analogous hydrocarbons, check out the Chime images of a few common simple
heterocylces and a few more complex natural heterocycles shown below.
Tetrahydrofuran
(THF)
Pyrrolidine
Piperidine
Morpholine
Chapter 3:
Conformations of Alkanes and Cycloalkanes
This page contains some examples of interesting polycyclic and / or heterocyclic molecules. When
looking at the Chime images, look at the types of ring systems that are present.
RANITIDINE:
C13H22N4O3S, mol.
wt.
=
314.41
g/mol
o
Physical properties: Solid, mp = 69-70 C. US patent is held by Allen and Hanburys.
The hydrochloride of Ranitidine is called Zantac, one of the most prescribed drugs in the western
world. Zantac is an off white solid, mp = 133-134 oC. It is soluble in acetic acid, water and
methanol,
sparingly
soluble
in
ethanol,
insoluble
in
chloroform.
Ranitidine is a histamine H2-receptor antagonist which inhibits gastric acid secretion.
Therapeutically it is used as an antiulcerative.
PRONTOSIL
:
C12H13N5O2S,
mol.
wt.
=
291.33
g/mol
o
The hydrochloride salt is an orange-red cyrstaline material, mp : 248-250 C, solubility: 1g in 400
ml water, much more soluble in hot water, soluble in alcohol, acetone, fats and oils.
Prontosil was original prepared as an "azo-dye" and used for dyeing wool fibres. However, it was
part of an in vivo study for antibacterial activity (found to be active against Gram-positive
infections) and became a prototype compound that led to the development of the important
sulphonamide antibacterials. Prontosil was first drug introduced to treat bacterial infections.
Therapeutically it is used as an antibacterial, but it is also used as a specific stain for carbonic
anhydrase in polyacrylamide gels.
PROMAZINE:
C17H20N2S,
mol.
wt.
=
284.43
g/mol
Physical properties: an oily liquid, having an "amine" odour. bp(0.3) : 203-210 oC.
Prepared by heating a xylene solution of phenothiazine and 3-dimethylamino-1-chloro-propane in
the presence of sodamide. US patent for Promazine is held by Rhone-Poulenc.
The hydrochloride salt, Prazine (also known as Talofen or Sparine) is a white/yellow crystalline
material that oxidises in air. One gram is soluble in 3 ml of water. it is also soluble in alcohols and
chloroform, insoluble in diethyl ether and benzene. Aqueous solutions are slightly acidic to litmus.
Therapeutically it is used as an antipsychotic and an antihistamine in man and as a tranquilizer for
animals.
NOVOCAIN:
C13H20N2O2.HCl, mol.
wt.
273.07
g/mol
Mifepristone terminates pregnancy within the first 9 weeks of gestation. Structurally it is very
similar to Norethindrone. The US patent is held by Rousell-UCLAF. Also known as RU-486 and
Mifegyne.
Therapeutically it is used as an abortifacient.
Chapter 7 : Stereochemistry
<>
Summary:
Despite what one may perceive from a printed page or even the computer screen you are now
looking at, most molecules are not 2D objects, they are 3D as a result of the spatial arrangement of
the atoms, groups and bonds. The interaction of molecules (reactions) which occur as the result of
collisions between these 3D objects in 3D space, can therefore also have 3D requirements and
characteristics. Stereochemistry is all about the 3D properties of molecules and reactions.
Isomer types
Types of Stereoisomers
Optical Activity
Fischer projections
Chapter 7 : Stereochemistry
Isomer types:
Compounds that have the same molecular formula but different chemical structures are isomers or
isomeric.
Depending on the type of difference between the structures, it is possible to classify isomers into
various
sub-types.
The following tree diagram contains questions that helps you to decide which isomeric relationship
applies.
If you "click" on the yellow named boxes, there is a link to a definition and an example.
Isomers are compounds with the same molecular formulae but that are structurally different in
some way.
It is important to be able to recognise isomers because there can have different chemical, physical
properties and biological properties.
Constitutional (or structural) isomers differ in the order in which the atoms are connected so they
contain different functional groups and / or bonding patterns:
example:
1-propanol,
2-propanol
and
ethyl
methyl
ether
(C 3H8O)
Stereoisomers contain the same functional groups and bond connectivities, they differ only in the
arrangement of atoms (or groups) in space.
Conformational isomers (or conformers or rotamers) are stereoisomers produced by rotation about
bonds, typically rapidly interconverting at room temperature:
example 1: butane : staggered (left) and eclipsed (center).The C2-C3 bond rotation is
animated (right). Try rotating the model to look along the C-C to see the two forms.
example 2: cyclohexane : chair (left) and boat (right).These two forms can be interconverted
by twisting the ring structure.
Configurational isomers are stereoisomers that do not readily interconvert at room temperature and
can (in principle at least) be separated. In practice it may not be a simple task.
Geometric isomers are configurational isomers that differ in the spatial position around a bond with
restricted rotation (e.g. a double bond):
E-2-butene and Z-2-butene
Optical isomers are configurational isomers that differ in the 3D relationship of the substituents
about one or more atoms
sure
you
can
assign
their
configurations
correctly.
are
not
mirror
images
or
superimposable.
Chapter 7 : Stereochemistry
Enantiomers
Molecules that are non-superimposable mirror images are enantiomers, look at the two molecules
shown below and set them up to show this. Note that your left and right hands are a pair of
enantiomers.
(R)-2-chlorobutane (S)-2-chlorobutane
You should be able to draw these molecules, as given below the Chime images, and indicate how
they are mirror images!
Enantiomers are known as chiral molecules (derived from the Greek meaning hand), therefore, a
molecule that is superimposable on its mirror image is said to be achiral.
You should be able to draw the two mirror images of an achiral molecule and then see how if you
rotate one of the images the two molecules are actually the same.
are
characterised
by
the
presence
of
stereogenic
centre.
Chapter 7 : Stereochemistry
(R)-2-chlorobutane (S)-2-chlorobutane
Note you should be learning to relate the chime images to the drawn images. More importantly
you should be able to reproduce the drawn images as that is what you will be expected to do on
exams or assignments!
The presence of a single stereogenic centre in a molecule results in a chiral molecule.
Molecules can, however, possess more than one stereogenic centre. Such molecules may or may
not be chiral.
Isomers of chiral molecules that possess two or more stereogenic centres, may be either
enantiomers or diastereomers (stereoisomers that are not mirror images).
(S,R)-2-bromo-3-chlorobutane (R,R)-2-bromo-3-chlorobutane
Diastereomers can have quite different physical and chemical properties from one another.
Isomers of achiral molecules, that possess two or more stereogenic centres, are known as meso
isomers (stereoisomers that are superimposable). You should be able to draw a pair of meso
isomers and see how one relates to the other by simple rotation.
Image A above is the mirror image of B, but can be seen to be the same as B once it has been
rotated. A quick way of recognising whether a molecule is achiral is to look for a plane of
symmetry.
In this case, even though a stereogenic centre is present in each molecule, a sample is optically
inactive as the optical activity of the two extremes of inversion averages out.
The larger the atom, though, the slower the pyramidal inversion and as a result many optically
active compounds for P and S have been prepared.
Chapter 7 : Stereochemistry
Optical Activity:
Optical activity is the ability of a chiral molecule to rotate the plane of plane-polairsed light. It is
measured using a polarimeter, which consists of a light source, polarising lens, sample tube and
analysing lens.
When light passes through a sample that can rotate plane polarised light, the light appears to dim to
the eye because it no longer passes straight through the polarising filters. The amount of rotation is
quantified as the number of degrees that the analysing lens must be rotated by so that it appears as if
no dimming, of the light has occurred.
Specific rotation is a physical property like the boiling point of a sample and can be looked up in
reference texts. Take a look at a problem.
Enantiomers will rotate the plane of polarisation in exactly equal amounts (same magnitude) but in
opposite directions.
Dextrorotary designated as (+), clockwise rotation (to the right)
purity
%
=
enantiomeric
100
excess =
[]mixture
enantiomer 1 /
[]pure
enantiomer2
sample
[R]
=
concentration
[S] = concentration of the S-isomer
of
the
R-isomer
Chapter 7 : Stereochemistry
knowing just by looking at a structure whether the assignment of (+) or (-) is correlated to a
particular isomer, R or S.
If the name of a compound includes both the sign of rotation and the designation R or S then the
absolute configuration of that compound is known.
Let's see how chemists can determine the relative configurations of optically active compounds by
chemically
interconverting
them.
The reaction of an alcohol with TsCl is known to occur with retention of configuration, that is the
group priority of the stereogenic centre has not been altered. The reaction of the tosylate with
nitrile occurs with inversion, as a result the group priority at the stereogenic centre has been altered.
The absolute configuration of the parent is known while only the relative configurations of the
tosylate and the nitrile are known. The mechanistic aspects behind this will be discussed in more
detail in the next chapter.
Chapter 7 : Stereochemistry
Example: chlorofluoroiodomethane
The stereogenic center is easy to spot, and the four attached groups are I (purple), Cl (green),
F(brown) and H (white), listed in priority order, highest to to lowest. Rotate the CHIME image
below so the you are looking along the C-H bond and the H is away from you, then determine the
direction of high to low priority. It decreases clockwise, so this is the R enantiomer.
Subrules:
Chapter 7 : Stereochemistry
Fischer Projections:
Fischer Projections are abbreviated structural forms that allow one to convey valuable
stereochemical information to a chemist without them having to draw a 3D structural representation
of a molecule. These representations are only used for molecules that contain stereogenic centers,
which are then represented as simple crosses.
They can be derived by considering the more accurate 3D representation using wedges and
assuming the convention that horizontal lines represent bonds coming out of the plane of the paper
and vertical lines represent bonds going behind the plane of the paper.
Memory
Aid
?
A student once told me that she remembered the relative arrangement of the bonds by the fact that
the horizontal bonds were coming out to hug her !
When relating one Fischer projection to another it may only be manipulated within the 2D plane in
which it is drawn (that is it may not be rotated within 3D space), and only rotated a total a 180o
Why can't you rotate it 90o? A 90o rotation is equivalent to breaking bonds and exchanging two
groups, which would result in the formation of the other enantiomer.
CAUTION Fischer projections are often confused with simpler Lewis diagrams. Lewis
diagrams, however, are not intended to give any stereochemical information!
Fischer projections a can be used to describe molecules with more than one stereogenic centre.
If a Fischer projection of this type can be divided into two-halves that are mirror images than the
molecule may be identified as a meso isomer.
Entender la estructura y enlazar las molculas orgnicas es fundamental para poder entender sus caractersticas,
propiedades y reacciones. Esto debido a que las caractersticas y las reacciones son controladas por interacciones entre
las molculas y cuyo comportamiento es dictaminado por los tipos de enlaces que se encuentran dentro de esas
molculas.
Aunque usted puede pensar que la mayora de los conceptos que encierra este tema es una revisin de sus cursos
anteriores de qumica general, muchos estudiantes no estn tan solidamente empapados de los conceptos bsicos de la
qumica y requieren de estos conocimientos bsicos para poder sobrevivir la aventura que a partir de este momento
experimentara, as que deber estar conciente de que usted comienza su curso de qumica orgnica con buenos
fundamentos. As pues usted ms adelante, entender la localizacin de los electrones, ya que este estos arreglos de
electrones son los que crean los enlaces entre tomos y las reacciones qumicas que se crean justamente por una
reorganizacin de estos electrones para formar nuevos enlaces.
Con el adecuado conocimiento del enlace qumico y otros conceptos bsicos conocidos.
Empecemos a analizar las estructuras qumicas de los principales grupos funcionales y familias, los
principales tipos de reacciones y aplicaciones que se realizan en la qumica orgnica.
Comenzaremos a caminar con la primera familia de la qumica orgnica que son los hidrocarburos y
dentro de ellos estn como los ms simples los alcanos.
Reactividad Qumica.
Hidrocarburos
Tipos de hidrocarburos
El petrleo, como fuente de suministro
Alcanos
Nomenclatura
Propiedades Fsicas
Estructure
Ismeros
Estabilidad
Reactividad
Anlisis conformacional
Ejemplos
Cicloalcanos
Nomenclatura
Propiedades Fsicas
Estructura
Reactividad
Termodinmica y estabilidad
Reacciones
Mtodos de obtencin
Tema: Estereoqumica
Resumen
Las estructuras moleculares que observamos en nuestros cuadernos de apuntes o en una
representacin en la computadora solo nos muestran a las estructuras en dos dimensiones, sin
embargo las molculas existen en tres dimensiones debido a la disposicin espacial de los tomos
que forman una molcula, estos arreglos espaciales de los tomos dan al mismo tiempo propiedades
especiales a las molculas orgnicas por lo que su adecuado conocimiento y anlisis es bsico para
la descripcin de las estructuras, as como en su impacto en las diferentes reacciones orgnicas. Su
anlisis implica el conocimiento de conceptos bsicos que se describen con detalle en este tema.
Tipos de Ismeros
Tipos de estereoismeros
Que es un estereoismero?
Enantimeros
Que debo conocer acerca de un Enantimero?
Diasteroismeros
Que debo conocer acerca de un Diasteroismero?
Actividad ptica
Cahn-Ingold-Prelog (nomenclatura R y S)
Proyecciones de Fischer
Tarea.
C7
C12
C14
C17
O16
O24 N23
(c) Arregle usted en sentido decreciente a sus longitudes de enlace las siguientes uniones:
C14-
C15
C15-C17
C17-C18
C1-O24
(d) Que tipo de enlace esta involucrado en las siguientes uniones C3-C4, C17-C18, C15-O16 y S21C22?
(e) Marque con un pequeo circulo los carbones primarios existentes en la estructura, con una X a
los secundarios y con un pequeo triangulo a los terciarios.
(f) Cinco son los elementos que integran esta estructura; mencinelos y ordnelos en funcin de su
electronegatividad.
(g) En la proyeccin; que indican las lneas obscuras y las rayadas y que tipo de proyeccin se esta
utilizando para representar esta estructura.
(h) Dentro de que familia de la qumica orgnica colocara usted a este compuesto.
understand the chemistry of life, we need to first understand the basics of general chemistry. So to
begin, here are some definitions:
matter - anything that occupies space and has mass (matter includes things that are solids,
liquids, gases)
mass - the amount of matter in an object
element - the most basic unit of matter; a substance that cannot be decomposed into
simpler substances by chemical or physical means
atom - the smallest component of an element having the chemical properties of the
element
protons - postively charged particles located in the nucleus of an atom (p+)
neutrons - uncharged particles in the nucleus of an atom
electrons - negatively charged particles that move around the nucleus (e-)
atomic mass - each element has an atomic mas which is the number of neutrons and
protons in the atom's nucleus
atomic number - each element has an atomic number which is the number of protons in
the nucleus of one of the element's atoms
molecule - a bonded collection of two or more atoms of the same or different elements
compound - a substance with constant composition that can be broken down into
elements by chemical processes
The elements that naturally occur in animals include (in order of descending percent body weight,
approx):
oxygen (65%)
carbon (19%)
hydrogen (10%)
nitrogen (3%)
calcium (1%)
phosporus (1%)
potassium (0.2%)
sulfur (0.1%)
sodium (0.1%)
chlorine (0.1%)
magnesium (0.1%)
manganese (0.1%)
iron (0.1%)
copper (0.1%)
iodine (0.1%)
Molecules can be subdivided into two main groups, those that contain carbon, organic molecules
and those that lack carbon, inorganic molecules. The chemistry of the organic molecules is
influenced primarily by the characteristics of carbon. Carbon atoms bond together with other
carbon atoms to form chains and rings of a wide range of lengths and configurations. Some
examples of organic molecules include:
carbohydrates (animals' main source of energy)
lipids (building blocks of fats, make up cell parts and supply energy)
proteins (structural material, hormones, enzymes, metabolic functions, endocrine functions)
nucleotides (building blocks of nucleic acids, DNA and RNA)
Tarea
Alkanes
# Carbon Name
Molecular Structural
Formula
Formula
Methane
CH4
CH4
Ethane
C2H6
CH3CH3
Propane
C3H8
CH3CH2CH3
Butane
C4H10
CH3CH2CH2CH3
Pentane
C5H12
CH3CH2CH2CH2CH3
Hexane
C6H14
CH3(CH2)4CH3
Heptane
C7H16
CH3(CH2)5CH3
Octane
C8H18
CH3(CH2)6CH3
Nonane
C9H20
CH3(CH2)7CH3
10
Decane
C10H22
CH3(CH2)8CH3
The parent name of the molecule is determined by the number of carbons in the longest chain.
In the case where two chains have the same number of carbons, the parent is the chain with the
most substituents.
The carbons in the chain are numbered starting from the end nearest the first substituent.
In the case where there are substituents having the same number of carbons from both ends,
numbering starts from the end nearest the next substituent.
When more than one of a given substituent is present, a prefix is applied to indicate the number of
substituents. Use di- for two, tri- for three, tetra- for four, etc. and use the number assigned to the
carbon to indicate the position of each substituent.
Branched Alkanes
Branched substituents are numbered starting from the carbon of the substituent attached to the
parent chain. From this carbon, count the number of carbons in the longest chain of the substituent.
The substituent is named as an alkyl group based on the number of carbons in this chain.
Numbering of the substituent chain starts from the carbon attached to the parent chain.
The entire name of the branched substituent is placed in parentheses, preceded by a number
indicating which parent-chain carbon it joins.
Substituents are listed in alphabetical order. To alphabetize, ignore numerical (di-, tri-, tetra-) prefixes
(e.g., ethyl would come before dimethyl), but don't ignore don't ignore positional prefixes such as iso
and tert (e.g.,. triethyl comes before tertbutyl).
Cyclic Alkanes
The parent name is determined by the number of carbons in the largest ring (e.g., cycloalkane such
as cyclohexane).
In the case where the ring is attached to a chain containing additional carbons, the ring is considered
to be a substituent on the chain. A substituted ring that is a substituent on something else is named
using the rules for branched alkanes.
When two rings are attached to each other, the larger ring is the parent and the smaller is a
cycloalkyl substituent.
The carbons of the ring are numbered such that the substituents are given the lowest possible
numbers.
Tarea.
ffsite.htm?zi=1/XJ&sdn=chemistry&zu=http%3A%2F
%2Fwww.faqs.org%2Ffaqs%2Fsci%2Fchem-faq
%2Fpart5%2F
Al abrir esta paguina aparecen mas apartados refiriendose a
otros conceptos interesantes en pequeas notas.
Sci.chem FAQ - Part 1 of 7
There are reader questions on this
topic!
Help others by sharing your
knowledge
From: Bruce Hamilton <B.Hamilton@irl.cri.nz>
Newsgroups: sci.chem
Subject: Sci.chem FAQ - Part 1 of 7
Date: Thu, 15 Jan 2004 22:06:54 +1300
Message-ID: <pslc00l3l7nii4m1686oarr4q2dtgq1l6c@4ax.com>
Reply-To: B.Hamilton@irl.cri.nz
Archive-name: sci/chem-faq/part1
Posting-Frequency: monthly
Last-modified: 22 October 1999
Version: 1.17
FAQ: Sci.chem
Editor: Bruce Hamilton
B.Hamilton@irl.cri.nz
This FAQ is posted monthly to the Usenet groups sci.chem, sci.answers and
news.answers, and the latest version should be obtained from any of those
groups, or from the Dejanews or Altavista WWW sites that also offer Usenet.
It can be obtained by FTP from the FAQ archive site at rtfm.mit.edu in the
pub/usenet-by-hierarchy/sci/chem directory, where other chemistry-related
FAQs are also archived as ascii files in their sub-directories.
The FAQ is also available, along with many other Usenet FAQs, on the WWW at
www.faqs.org, in both ascii and simple hypertext formats. Due to propagation
delays, some WWW and archive sites may not contain all parts of the latest
version, but a WWW search engine should locate those parts at other sites.
Changes:
- revised WWW sections.
- updated various email addresses,
- updated references
Subject: 1. Dedication
This FAQ is dedicated to the memory of the late Larry Lippman, who departed
from this group ( and life ) in 1991. His superb posts on a wide range of
chemical topics were both informative and entertaining. He established the
sci.chem tradition of friendly, authoritative, and accurate answers to
many chemistry-related questions.
Dedication
2.
3.
Contributors
Jason Bruce Chin
Jim Corton
Neil Flatter
Bruce Hamilton
Vince Hamner
Theodore Heise
Knut Irgum
Jim Oliver
Yogi Shan
Mark Perks
Dave Young
4.
Table of Contents
5.
Sci.chem
5.1 What topics does sci.chem cover?.
5.2 What guidelines are available about posting to sci.chem?.
5.3 Should I post my homework question?.
5.4
5.5
5.6
5.7
5.8
5.9
5.10
5.11
5.12
5.13
5.14
5.15
5.16
5.17
6.
Part 2.
7.
*
8.
Laboratory
8.1 Where
8.2 Where
8.3 Where
8.4 Where
8.5 Where
8.6 Where
and
can
can
can
can
can
can
9.
10.3
10.4
10.5
10.6
10.7
Where can I
Where can I
What is the
Where can I
Are contact
Part 3.
11. Traditional
11.1 Where
11.2 Where
11.3 Where
11.4 Where
11.5 Where
11.6 Where
11.7 Where
11.8 Where
11.9 Where
Specialist
can I find
can I find
can I find
can I find
can I find
can I find
can I find
can I find
can I find
12. Nomenclature
12.1 What are CAS Registry Numbers?.
12.2 What are the correct names of recently-discovered elements?.
12.3 What is the nomenclature system for CFCs/HCFCs/HFCs?.
12.4 How can I get the IUPAC chemical name from traditional names?.
12.5 What does "omega-3 fatty acids" mean?.
12.6 What is Conjugated Linoleic Acid?.
12.7 What are "heavy" metals?.
12.8 What is the difference between Molarity and Normality?.
12.9 Where can I find the composition of common named reagents?.
13. Illicit and Government-Controlled Substances
13.1 What news groups/mailing lists discuss illegal drugs?.
13.2 Where can I obtain a list of illegal drugs?.
13.3 What is the chemical structure of common illegal drugs?.
13.4 How do I obtain chemical information on illegal drugs?.
13.5 Where are the synthesis instructions for illegal drugs?.
13.6 Should I post detailed recipes for illegal chemicals?.
13.7 What news groups/mailing lists discuss explosives?.
13.8 What is the chemical structure of common explosives?.
13.9 How do I obtain chemical information on common explosives?.
13.10 What news groups/mailing lists discuss pyrotechnics?.
14. Academic Course Information
**
14.1 Where do I find information on US courses?.
**
14.2 Where do I find information on other nations' courses?.
Part 4.
15. Chemical Demonstrations
15.1 Are there any good compilations of demonstrations?.
*
15.2 What are good outdoor demonstrations for under 12s?.
*
15.3 What are good outdoor demonstrations for over 12s?.
*
15.4 What are good indoor demonstrations for under 12s?.
*
15.5 What are good indoor demonstrations for over 12s?.
15.6 How do I safely perform the Glowing Pickle experiment?.
15.7 How do I make Slime?.
16. Laboratory
16.1 What
16.2 What
16.3 What
Procedures
are the best drying agents for liquids and gases?.
is the effect of oven drying on volumetric glassware?.
does the Karl Fischer titration measure?.
16.4
16.5
16.6
16.7
What
What
What
What
17. Preparation
17.1 Where
17.2 Where
17.3 Where
chemicals
I find laboratory-scale procedures for organics?.
I find laboratory-scale procedures for inorganics?.
I find industrial chemical process details?.
What
What
What
What
24. Extraction
24.1 What
24.2 What
24.3 What
24.4 What
Techniques
is Solvent Extraction?.
is Solid Phase Extraction?.
is Supercritical Fluid Extraction?.
traditional process extracted perfume from flower petals?.
32. References
Subject: 5. Sci.chem
5.1
satisfy your curiosity, then carefully outline your problem, list the
information resources you have investigated, and post only to the most
appropriate group. If it is the wrong group, somebody will point you to the
correct one. Do not expect to receive the actual answer, most readers will
carefully consider your request, and usually frame a response to ensure that
you need to perform some work before you can answer your own question. The
most obvious technique is to respond with a similar worked example which is
sufficiently different to ensure that you can not simply plug in numbers and
arrive at your correct answer. Often posters will point to specific library
resources for you to locate and read.
Also, remember that posters are not obliged to provide only correct answers,
they can deliberately introduce errors to ensure direct copying without
comprehension results in the wrong answer - it is not their homework :-).
Teachers can identify dramatic changes in students' writing styles, and a
quick search using Alta Vista or DejaNews can readily confirm their
suspicions. Do not expect sensible or accurate responses if you post from
anonymous servers.
5.4
Sci.chem is the most popular chemistry-related group, and thus would provide
the largest target audience. However, the appropriate group for advertising
vacancies and seeking employment is misc.jobs.fields.chemistry. Please post
CVs, Resumes, and Job Descriptions there, and frequently review the group.
Misc.jobs.fields.chemistry will have a very small readership, so it may be
worthwhile for those offering employment to also select a few relevant groups
and post a brief pointer to the post listing essential information. If you
have posted your resume or CV to m.j.f.c, then you just have to wait and hope
those with vacancies are reviewing the group. Do not post pointers to your CV
or Resume to other groups. Posting your CV/Resume to sci.chem may annoy some
readers who could be prospective employers in the future, so you have to
assume that those currently offering employment will review m.j.f.c. Also,
remember that all posts ( including CVs and Resumes posted to m.j.f.c ) may
be archived at sites such as DejaNews, and thus available for scrutiny by
future employers, unless you use the X-No-Archive header.
5.6
No. The onus is on you to obtain access to the correct group. As hard disk
storage prices are plummeting, you should be able to encourage your access
provider to carry more groups :-). If your employer restricts you to sci.*
comp.* and other boring groups, you may have to seek out a commercial
access provider. Be assured that you are not the first to encounter this
problem, and there are various ways you can access newsgroups using other
Internet facilities besides direct Usenet access. Check out the news.*
groups for information on alternative methods of Usenet access.
5.7
No. Once again the onus is on you to obtain the texts. We have tried to
ensure that there are several choices to help minimise the problem. The
advantage of expending effort to obtain the reference is that it is likely
to provide a more comprehensive answer, and will enhance your understanding
of the subject. If the reference is obscure, then a carefully-constructed
post requesting the specific information you require is acceptable, but
you should also state that you have tried to obtain the information, and
perhaps suggest email replies if you believe other readers will not be
interested. Chemistry teachers and other chemistry professionals may also
have their personal copies of some of the reference texts, and may permit
you to use their copy, if asked politely.
5.8
No. Most countries have signed the Berne Convention, and adjusted their
national laws to reflect the concept that copyright ownership is the
property of the author of any piece of work. Thus any redistribution or
reproduction of that work has to have the author's express permission.
The act of posting to Usenet does carry an implicit acknowledgment that
followup articles will requote parts of the original for clarity, and
perhaps will be subsequently crossposted to additional groups and archived
at DejaNews or other archive sites. If an author of a post or article does
not want their post archived, your software may permit you to select the
"X-No-Archive" header and, if the software does not support that header,
you can also add it manually as the first line of a post, but some archive
sites may still ignore that header and archive the post.
The copyright of the article is still owned by the original author, and
consent is required before distribution extends outside of Usenet - including
placing it on the WWW. Most posters will readily give permission if asked.
Commercial WWW sites also have specific copyright notices just to remind
readers that the material can not be redistributed. "Fair Use" is a very
specific and limited concept, and does not permit significant copying of
copyrighted material - it expects the user to selectively edit and repost
only the minimum necessary material. Two FAQs ("Copyright Myths" and the
more detailed "Copyright" ) are posted to news.newusers.questions,
news.admin.misc, and some other groups that discuss intellectual property.
5.9
Not without their consent. Email the expert and ask if you can identify them
in sci.chem. In general, people who email information to you will want
complete control over their exposure on Usenet. Often they do not want a
the current size of sci.chem is easily handled, and most threads of interest
can be captured as they pass.
5.15 How do I create a sub-group for my pet topic?.
First of all, discuss your idea extensively in sci.chem and other relevant
groups and mailing lists, ensure you have sufficient support for your
proposal, and take note of all comments, whether positive or negative.
The next stages are well documented in a FAQ available in news.groups.
Basically, you email group-advice@uunet.uu.net, who will help you prepare
the charter and Request For Discussion, and may even provide a mentor to
guide you through the process.
If the proposal has an additional vote that could affect another group by
renaming or changing the hierarchy, return to that group and consult the
participants to ensure there is support for any proposed changes prior
to issuing the RFD. Group advice is not mandatory, so if the added vote
is contentious, drop it. Post the RFD twice, and remind people to ensure
they cross post to news.groups, even if they do not read that group, as
that is where all post-RFD discussion is supposed to occur. Take note of
the discussion in news.groups and other groups where you posted the RFD,
and modify the RFD, if appropriate, and post it again. Then follow the
guidelines for the actual vote, others will administer the vote and create
the groups, if they pass.
5.16 Where are the sci.chem archives?.
Given the nature, number, and diversity of sci.chem posts, no formal
archives exist, however the Usenet archives at DejaNews on the WWW will
contain most of the articles for the last couple of years,
http://www.dejanews.com/
There are also several other WWW sites that offer access to, and
keyword searching of, recent Usenet posts. One site is Alta Vista.
http://altavista.digital.com/
The total number of articles that you will see in sci.chem will depend
on how your system administrators have set the News system. If they set
a short Expire time, and set the software to ignore the Expiry date line,
you may actually miss some articles that have long propagation times.
The best solution is to politely ask the administrators to increase the
Expire time - usually they are more sympathetic to requests to increase
Sci.* expire times than they are to requests for longer Alt.* expire times.
Sometimes they just can't oblige, so you may have to read the group more
frequently, but please check DejaNews before posting requests for old
articles.
It should also be remembered that Usenet archive sites like DejaNews
will retain all of your posts - unless you set the "X-No-Archive" header
appropriately. Some posting software does not have the facility to set
such headers, but it can be added manually to the first line of a post.
It has been reported that some employers now review such archive sites for
posts when evaluating job applications. Although DejaNews honours the
"X-No-Archive" header, that does not mean that all archiving sites will,
so your posts may still be hiding somewhere on the Internet.
5.17 Who was Larry Lippman?.
When sci.chem was formed (1988?), there were only a few posts per week, and
a considerable number were requests for information. Larry Lippman soon
established his superb practical and theoretical chemical credentials, and
set about responding to those plaintive pleas for information. His posts
were excellent examples of informative, educational responses delivered in
a friendly, helpful style. His posts demonstrated how knowledgeable sci.chem
posters could respond to requests in such a way that all readers would
understand, regardless of formal chemical training. He died in late 1991
in his early 40s. Unfortunately, only a few of his posts to sci.chem have
survived. If you have any of his posts I would appreciate a copy, as I am
collecting them to be made available as a single "Lippman posts" file.
These terms apply to well-known reference texts. Note that those with a "*"
are also available from commercial database suppliers and/or as CD-ROMs.
The electronic versions may be accessible via an institution library, if the
library does not have the hardcopy version available.
* Beilstein = Handbuch der Organischen Chemie [1].
* Bretherick = Handbook of Reactive Chemical Hazards [2].
* Chem.Abs. = Chemical Abstracts [3].
Cotton and Wilkinson = Advanced Inorganic Chemistry [4].
Fieser & Fieser - Reagents for Organic Synthesis [5].
* Gardner = Chemical Synonyms and Trade Names [6].
Gmelin = Handbuch der Anorganischen Chemie [7].
Goodman & Gilman = The Pharmacological Basis of Therapeutics [8].
* Hawley = Condensed Chemical Dictionary [9].
* Heilbron = Dictionary of Organic Compounds [10].
* Kirk Othmer = Kirk Othmer Encyclopedia of Chemical Technology [11].
Lange = Handbook of Chemistry [12].
* Martindale = The Extra Pharmacopoeia [13].
McKetta = Encyclopedia of Chemical Processing and Design [14].
Mellor = Comprehensive Treatise on Inorganic and Theoretical Chemistry [15].
Mutilated by:
Neil Flatter
Lev A. Gorenstein
Theodore Heise
Mark Perks
Bruce Hamilton
Searching
There are several well-known search engines available on the WWW that will
provide updated searches for keywords. Because of the huge expansion of the
WWW, I've decided to select some sites and allow users to use search
engines and/or web crawlers to locate resources. If you find a real
treasure house of chemical goodies, email me the address and I'll check it
out. It is important to realise that many of the WWW search engines are
complementary, and so it is useful to utilise several when trying to locate
information on the web - good places to start are directories of various
WWW search engines.
http://home.netscape.com/home/internet-search.html
http://cuiwww.unige.ch/meta-index.html
Free search engines include:http://altavista.digital.com/
http://www.google.com/
http://www.lycos.com/
http://www.yahoo.com/
http://infoseek.go.com/
Alta Vista
Google
Lycos
Yahoo
Infoseek
http://www.excite.com/
http://www.webcrawler.com/
Excite
Webcrawler
The obvious first places to start are Dialog and STN. The range of chemistryrelated databases are extensive. There are several full-text databases of
patents, full-text newspapers and journals, and many specialised databases.
- industry-specific
Aluminium Industry Abstracts, Paperchem
- subject-specific
Fine Chemicals Database, Chemical Engineering and
Biotech Abstracts
- chemical properties
Beilstein, Heilbron, Merck Index, Agrochemicals
Handbook
- location-specific
IMS World R&D focus.
- chemical market
Chemical Business Newsbase, Chemical Industry Notes,
Freedonia Market Research.
If you plan on using Knight Ridder's lower cost Knowledge Index, ensure that
the databases you are interested in are available on KI, as not all Dialog
databases are.
With nearly 200 databases on STN and approximately 500 on Dialog, they both
offer access to a wide range of information. For more specialist information,
accessing individual businesses is required, and they can provide specialist
sales, marketing and technical support for their products - many such
businesses are now accessible via the WWW. There are also the various
registry companies like Thomas that list chemical and equipment suppliers,
and who also offer a free evaluation period:http://www.thomasregister.com/
7.4
Both Dialog and STN offer commercial access to US and International patents
online, many with full text - however the international ones, especially
those devoted to capturing the current status of patents can be expensive,
so ensure your searching skills are honed if you wish to avoid a large
bill.
http://patent.womplex.ibm.com/
http://www.patents.ibm.com/
A new site that offers free searching of the last 20+ years of US
patents, and also provide the abstracts, some images, and the claim
summary free. Complete copies of the patents can also be ordered.
It has a good search engine, and probably should be the first site to
visit, but note that it requires a browser that supports frames
(eg version 3 of Netscape or Internet Explorer).
http://metalab.unc.edu/patents/intropat.html
STO Patent retrieval service
Gregory Aharonian has struggled for several years to provide a free,
comprehensive patent title service. This excellent free service offers
the titles of chemical, mechanical, or electrical patents via email
to subscribers. Recently he also offered one years worth of patent
abstracts, but requires some financial donations to expand the
service. The abstracts are freely retrievable by patent number (sorry
no searching yet, that needs the big donations). For subscription info,
send 'help' to patents@world.std.com.
http://www.uspto.gov/patft/index.html
USPTO/CNIDR Patent Project
This page provides access to both the U.S. Patent Bibliographic
Database, which includes bibliographic data from 1976 to 1997, and
the AIDS Patent Database, which includes the full text and images
of AIDS related patent issued by the U.S., European and Japanese
Patent offices.
7.6
ftp://kekule.osc.edu/pub/chemistry/
Jan Labanowsky's server, also contains an archive of the computational
chemistry mailing list.
ftp://qcpe6.chem.indiana.edu/
QCPE archive
ftp://oak.oakland.edu/pub/simtelnet/
Dos and Windows public domain and shareware
7.7
LISTSERV@Beaver.Bemidji.MSUS.edu
Chemistry laboratories (both academic and research), students'
experiments (high school, college and university), classroom
demonstrations and shows for the public of chemical processes,
small-scale chemical
In general, most WWW sites will also contain email addresses that they
can be contacted through.
http://www.acs.org/
The American Chemical Society homepage provides access information,
and additional email support is available via the following:division@acs.org
ACS Division information
expo@acs.org
ACS expositions
meminfo@acs.org
ACS membership information
natlmtgs@acs.org
ACS national meeting information
rxnt@acs.org
Reaction Times (college newspaper)
reglmtgs@acs.org
ACS regional meeting information
slga@acs.org
ACS state and local government affairs
http://www.rsc.org/
marketing@rsc.org
The UK Royal Society of Chemistry, WWW and email address.
http://sci.mond.org/
The UK Society of Chemical Industry.
http://www.gdch.de/
pr@gdch.de
The German Chemical Society (Gesellschaft Deutscher Chemiker, GDCh)
http://wwwsoc.nacsis.ac.jp/csj/index-e.html
The Chemical Society of Japan ( English index )
7.9
Argus Chemicals
Dow Chemicals
Eastman Chemicals
GE Plastics
Hoechst
Eli Lilly
Monsanto
Quality Chemicals
Rohm and Haas
Sigma, Aldrich and Fluka
Sumitomo Chemicals
Check out the FAQs in rec.pyrotechnics and alt.drugs, they may also list
some legal suppliers. With the rapid growth of the WWW, it is usually
a good idea to conduct a search to locate suppliers, and you could try
the Chemsources or Thomas Register sites to locate addresses.
http://www.chemsources.com/
http://www.thomasregister.com/
Use of WWW search engines and specific terms like "biochemicals"
will locate the WWW and email addresses of speciality suppliers
7.11 How can I contact equipment suppliers
Check out the FAQs in rec.pyrotechnics and alt.drugs, they
some legal suppliers. With the rapid growth of the WWW, it
a good idea to conduct a search to locate suppliers on the
and using the Thomas Register site to locate suppliers not
http://www.thomasregister.com/
Thomas Register
http://www.sigma-aldrich.com/
Sigma, Aldrich, Fluka and Supelco
http://www.fisherscientific.com/
Fisher Catalogue
Mutilated by:
8.1
Neil Flatter
Lev A. Gorenstein
Theodore Heise
Mark Perks
Bruce Hamilton
Manufacturers are required by OSHA to provide MSDSs for the chemicals they
produce, but most include liability disclaimers. For MSDSs obtained from
online sources, the user must be sure the MSDS meets his/her needs. As with
most information obtained from the Internet, use at your own risk!. If you
don't know how to interpret the data, find an expert to explain the
significance of the information presented. Because the number of WWW sites
with MSDS are changing all the time, it is often preferable to use a WWW
search engine to find the latest sources of data sheets.
http://hazard.com/msds/
http://haz1.siri.org/
The comprehensive Vermont SIRI location is an excellent first port of
call when searching for chemical safety information. ~180,000 MSDS
http://msds.pdc.cornell.edu/issearch/msdssrch.htm
The Cornell site mirrors the Vermont SIRI site and also contains the
US Department of Defence CD-ROM MSDS. ~325,000 MSDS
http://www.ilpi.com/msds/
The Dept. of Chemistry, University of Kentucky, maintains an up-to-date
" Where to find MSDS on the Internet " site pointing towards over
thirty useful locations.
http://chemfinder.camsoft.com/
CambridgeSoft Corporation's Chemfinder free searching server will also
locate safety information for chemicals, including ~60,000 MSDS.
http://www.fisherscientific.com/
The Fisher Scientific Chemical Catalog is available online. In addition
to MSDSs, you can order chemicals.
http://ulisse.etoit.eudra.org/Ecdin/Ecdin.html
Environmental Chemicals Data and Information Network in Italy provides
a searchable database with 120,000 MSDS.
8.2
http://hazard.com/msds/
http://haz1.siri.org/
The comprehensive Vermont SIRI location is an excellent first port of
http://www.acgih.org/
The most well-known list of occupational exposure limits is the annual
list of TLVs and BEIs compiled by the ACGIH, who also offer a diverse
range of reports and pointers to other sources of information.
http://law.house.gov/cfr.htm
Recent (but perhaps not most current, but it is being updated) site
for the Code of Federal Regulations. Title 29 of the CFR (Labor)
section 1910.1000 lists OSHA's permissible exposure limits (PELs)
for air contaminants.
8.4
http://www.christie.ab.ca/safelist/
Carolla Christie of Christie Communications maintains an excellent
list of environmental and occupational health and safety information
resources available on the Internet.
http://www.sra.org/riskanal.htm
RISKANAL mailing list.
discusses environmental and occupational health and safety issues,
particularly those associated with college and university campuses,
although a wide range of subjects is encouraged.
8.6
Many of the Chemistry Overview WWW sites in Section 7.2 also have safety
sections with extensive numbers of pointers to WWW sites. Some US
Government departments ( OSHA, EPA, NIH ) have WWW sites with information,
which can be accessed directly, or via some of the sites in Section 7.12.
http://dchas.cehs.siu.edu/
The ACS division of Chemical Health and Safety homepage.
http://www.setac.org/
The Society for Environmental Toxicology and Chemistry
http://www.aiha.org
The American Industrial Hygiene Association
The WWW site below has large numbers of pointers to other sites with
extensive ranges of information on chemical, laboratory, and general
safety issues.
http://www.christie.ab.ca/safelist/
Carolla Christie of Christie Communications maintains an excellent
list of safety information resources available on the Internet.
The list is also posted to the SAFETY mailing list above.
Most governments have a patent office, and there are usually branches in main
centres. If you are able to obtain access to the patents at the patent office,
and are familiar with patent codes, or know the patent number, the cost will
be lower than using a patent attorney. If you do not know how to search for
patents, and your time is valuable, you will find that using a patent
attorney will be very cost effective. An excellent guide to the general
concepts of patents and what you can expect to find, along with the
advantages and disadvantages, is " What Every Engineer Should Know About
Patents" [1].
9.3
The chemicals usually found in home chemistry sets can usually be purchased
at the shop where the set was obtained, or the local hardware shop or
pharmacist, provided the chemical is not subject to government or state
restrictions. Many chemicals are only available to approved purchasers.
If the chemical is used for a hobby, then it is very likely the FAQ for that
Usenet group ( eg rec.pyrotechnics ), will contain information on suppliers.
Most national chemical societies publish an annual listing of suppliers with
their journals. Standard trade directories ( eg Chem Sources [2,3] and OPD
Chemical Buyers Directory [4] ) list companies who specialise in chemicals,
Once you have checked the catalogues, and checked the standard texts above,
then more specialised compilations should be checked. For spectral
properties, there are several large compilations of detailed spectral
properties, including infra-red [35-37], NMR [38-40], and mass-spec [41,42].
These are usually located near the instruments, rather than in the library,
however the NIST IR and mass spectral libraries are accessible via the WWW
( refer Section 7.2 ).
Most transportation safety compilations and MSDS also list common physical
properties, as do the most of the encyclopedia sets ( refer Section 9.5 ).
More specialised information is usually found in specialist books or
journals, such as the Journal of Chemical and Engineering Data.
9.7
Both Kirk Othmer and Ullmann tabulate production data, and identify
major manufacturers, and more recent information is found in monographs
in CMR. C&EN also tabulates production data for the major industrial
chemicals and publishes an annual listing of the top 50 chemicals. Lists of
manufacturers of chemicals are found in compilations such as Chemical
Sources [2,3] and trade directories. There are also industry organisations
such as the Chemical Manufacturers Association that maintain records of
production. Specialist industry journals usually provide annual surveys
of production and capacity. Government departments ( often the Dept. of
"Trade & Industry" or "Commerce" ) also compile national production
statistics.
9.8
Earnshaw [48], and "The Elements" by Emsley [49], also provide good
discussions, and Gmelin provides a fairly comprehensive discussion of
discovery of each element. In each of the above, the discovery of each
element is taken in isolation. The best general overview that provides a
cohesive framework explaining the overall progression of discoveries, is
"Discovery of the Elements" by Weeks [50], and it should be available in most
libraries. For the more recent elements, there usually are brief reports and
discussions in C&EN and the Journal of Chemical Education.
9.11 What inspirational books about chemistry should I read?
Do they exist :-)?. You could try "The Chemical Bond: Structure and Dynamics"
edited by A.Zewail [51]. It contains articles by several Nobel Laureates.
If you want to be entertained, and only have time for a short read, try the
"Chemistry in the Next Century" [52] article in Industrial and Engineering
Chemistry written in May 1935 by Thomas Midgley, Jr.. He was responsible for
the discovery and development of CFCs and alkyl lead octane enhancers for
gasoline - two chemical developments that became so pervasive and useful
that their use resulted in unintentional environmental pollution.
For a brief story about their discovery, try "Midgley - Saint or Serpent"
[53] in Chemtech. It confirms that old saying " Luck is when preparation
meets opportunity ".
The very first question you should ask is, "Am I qualified to assess
the data?". If the answer is no, then your best option is to locate somebody
who is. This can be a Health and Safety Officer, staff of an appropriate
government organisation (eg OSHA, NIOSH ), or a specialist consultant.
Most institutions have a policy of ensuring workers are given sufficient
information about hazards to ensure they can make an informed decision.
There are several major compilations that are usually found in libraries,
including RTECS, Sax, and the three-volume Sigma-Aldrich Library of
Regulatory and Safety Data [7]. In general, because safety information can
become obsolete rapidly, these should only be used as an introductory guide,
and they should be complemented with either an on-line search or consultation
with
an expert. Detailed information for unusual chemicals is often difficult to
locate in the published literature, and may only be available to qualified
professionals in the health and safety fields. Sometimes the toxicity has to
be inferred from published information on related compounds, and such
assessments should always be performed by experts.
10.3
" All substances are poisons. There is not one that is not a poison. The
correct dose differentiates a poison and a remedy". (Paracelsus 1493-1541)
The McGraw Hill Encyclopedia of Science and Technology [11] lists the
following table:
"Approximate Median Lethal Doses of Some Toxins per kg of Bodyweight"
Toxin
Dose
Test Animal
tetanus
1 nanogram
mouse, probably human
botulinal neurotoxin
1 nanogram
mouse, human
shigella
1 nanogram
monkey, human
shigella
1 microgram
mouse
ricin
1 microgram
human
diphtheria
100 nanograms
human
diphtheria
1.6 milligrams
mouse
Ricin is a toxin lectin and hemagglutinin isolated from the castor bean.
Merck reports the lethal dose in mice as 1 microgram of ricin D nitrogen
(ip) per kg, and that ricin molecular weight is about 65,000. Ricin has
been shown to contain four lectins, of which the RCL III (aka Ricin D )
and RCL IV are the toxins. Merck also reports the following LD50 per kg
of bodyweight:Toxin
palytoxin
( from coral )
( C129H223N3054 )
saxitoxin
( from shellfish )
( [C10H17N7O4]2+ )
tetrodotoxin
( from globefish )
aflatoxin M1
aflatoxin M2
aflatoxin B1
aflatoxin B2
aflatoxin G1
aflatoxin G2
Dose
60 nanograms
450
"
50-100
"
3-5 micrograms
10
"
263
"
10
"
332
1.2
364
1.6
784
3.4
micrograms
milligrams
micrograms
milligrams
micrograms
milligrams
Test Animal
dog (iv)
mouse (iv)
"
(ip)
mouse (iv)
"
(ip)
"
(oral).
mouse (ip)
duckling (oral)
"
"
duckling (oral)
"
"
"
"
"
"
There are a lot of myths about the occupational use of contact lenses, many
of which relate back to a Bethlehem Steel welder in Baltimore who, on the
26 July 1967, accidentally caused an arc flash that hit his hard contact
lens. He waited until the next day to report eyesight problems, and an
ophthalmologist found severe ulcerations on his cornea, but attributed
the damage to the wearing of the hard lenses for 17-18 hours after the
incident. The cornea healed completely in a few days, with no permanent
vision loss, and investigators found no link between the damage and the
arc flash, but the myth of the welder removing parts of the cornea with
the lens, and consequently being permanently blinded, continues [14].
The banning of contact lenses from modern chemical laboratories is being
reconsidered in the light of increasing evidence that case-by-case
evaluations are more appropriate. Routine wearers of contact lenses may
suffer " spectacle blur " when they switch to spectacles, and this temporary
reduction in visual efficiency could result in the misreading of labels.
Contact lenses are not eye protection devices, and OSHA believes that
The most likely place is near to an instrument. These are not usually
in general technical libraries, but are kept near the instruments.
A polite request to the person in charge of the instrument should identify
who to contact for permission to use the library or database. There is
some spectral information in reference texts, such as the Rubber Handbook
and the Merck Index, but most compilations are now so large that they cover
several volumes. There are several compilations that are available
commercially, either in hard copy (HC) or CD-ROM (CD) - which is usually
more expensive because of the included searching software. Chemical
manufacturers, such as Aldrich, may also sell spectral libraries, eg
IR $495(HC) [1], FT-IR $875(HC) or $1578(CD) [2], 60MHz H1 NMR $495(HC) [3],
and 300MHz H1 + 75MHz C13 NMR $1072(HC) [4], as well as offering
compilations from government agencies, eg the NIST/EPA/NIH Mass Spectral
database $1320(CD)[5]. The databases are also sold by several instrument
manufacturers. One commercial supplier of spectral information ( Fiveash
Data Management, Inc. ) may be accessible via the Internet [6].
11.2
and Dioxin, and " Science of the Total Environment also covers many aspects.
Government agencies such as the EPA also publish large amounts of
information, and many environmental groups also provide significant amounts
of technical information. There are a range of specialist texts that cover
specific pollutants, eg "Metals and their Compounds in the Environment:
Occurrence, Analysis and Biological Relevance" [35].
The sci.environment Usenet group may well be a better place to request
environmental chemistry information than sci.chem, but please remember
to move discussions to talk.environment.
11.5
The best single volume remains Shreve's "Chemical Process Industries" [52].
There are three major multi-volume encyclopedias, Kirk Othmer, Ullmann,
and McKetta, that cover many aspects of industrial chemistry and at
least one is usually available in a public library. There are also several
journals that provide good overviews of industrial chemistry, the easiest
to read being C&EN, and Chemtech. Research is usually published
in Industrial and Engineering Chemistry ( which is an excellent source
for historical research ), and specialist chemical engineering journals.
11.9
When chemicals are first encountered by the Chemical Abstracts Service, they
are assigned a unique number when they are registered. These numbers are not
related to any structure or property of the molecule, they are arbitrarily
assigned. It should be remembered that occasionally a compound may be
accidentally assigned two or more numbers - especially industrial products
that have not been completely characterised. When this is discovered, one of
the numbers is no longer used. The numbers usually take the form of
[xx-yy-z to xxxxxx-yy-z] and square brackets are often used in monographs to
identify the CAS Registry Number [RN]. The easiest way to locate the CAS RN
for commercially-available chemicals is to look in suppliers catalogues
( eg Aldrich) or compilations ( eg Merck or Hawley ), almost all chemical
texts now list the RN, and several ( eg Merck Index and Aldrich ) have a
cross-reference Index. The RN is extremely useful for on-line searching of
Chemical Abstracts and several other popular chemistry-related databases,
but is not particularly useful for the hardcopy version, except to confirm
compound identity.
12.2
Mendelevium
Nobelium
Lawrencium
Md
No
Lr
D. Mendeleev (Russia)
Nobel Institute (Sweden)
E. Lawrence (USA)
104
105
106
107
108
109
Rutherfordium
Dubnium
Seaborgium
Bohrium
Hassium
Meitnerium
Rf
Db
Sg
Bh
Hs
Mt
E. Rutherford (NZ)
Dubna = Russian Research Centre
G. Seaborg (USA)
N. Bohr (Denmark)
Latin name for German state of Hesse
L. Meitner (Austria)
The CFC naming system was developed by T.Midgley,Jr. and A.L.Henne in 1929,
and further refined by J.D.Park. Originally, organic molecules that contained
Chlorine and Fluorine were all referred to as CFCs. Today, the group is
subdivided into CFCs, HCFCs, and HFCs. The naming system consists of:CFC-01234a
where 0
1
2
3
4
a
=
=
=
=
=
=
If the compound is cyclic, then the number is prefixed with "C". There are
several other refrigerants, some of which are hydrocarbons, hydrocarbon
blends, or CFC blends. Full details of the nomenclature system are specified
in ANSI/ASHRAE Standard 34-1992 with additional annual supplements. Chemical
names are frequently used in place of the numbers for common materials
- such as trichloroethylene and chloroform. The specified ANSI/ASHRAE
prefixes were FC ( FluoroCarbon ), or R ( Refrigerant ), but today most are
prefixed by more specific classifications - such as CFC, HCFC, and HFC.
CFC-11
CFC-12
CFC-113
HCFC-22
HCFC-123
HCFC-123a
HFC-23
HFC-134
HFC-134a
R-20
R-22B1
R-1120
R-1150
R-C316
CCl3F
trichlorofluoromethane
CCl2F2
dichlorodifluoromethane
CCl2F-CClF2 1,1,2-trichlorotrifluoroethane
CHClF2
chlorodifluoromethane
CHCl2-CF3
2,2-dichloro-1,1,1-trifluoroethane
CHClF-CClF2 1,2-dichloro-1,1,2-trifluoroethane
CHF3
trifluoromethane
CHF2-CHF2
1,1,2,2-tetrafluoroethane
CH2F-CF3
1,2,2,2-tetrafluoroethane
CHCl3
chloroform
CHBrF2
bromodifluoromethane
CHCl=CCl2
trichloroethylene
CH2=CH2
ethylene
C4Cl2F6
1,2-dichlorohexafluorocyclobutane
[75-69-4]
[75-71-8]
[76-13-1]
[75-45-6]
[306-83-2]
[354-23-4]
[75-46-7]
[359-35-3]
[811-97-2]
[67-66-3]
[1511-62-2]
[79-01-6]
[74-85-1]
Another technique for naming CFCs uses the addition of 90 to the CFC number
to produce a "def" number which corresponds to the CHF composition. If
(e + f) < (2d + 2), then additional atoms are required for saturation. This
technique has been described in detail in the Journal of Chemical Education
[3].
ASHRAE
+90
Empirical Composition
C H F
(+Cl)
Formula
CFC-11
CFC-12
HCFC-22
HCFC-123
HFC-134a
101
102
112
213
224
1
1
1
2
2
1
1
2
1
2
2
3
4
3
2
1
2
-
CCl3F
CCl2F2
CHClF2
CHCl2-CF3
CH2F-CF3
where 0
1
2
3
=
=
=
=
Halon-1211 CBrClF2
Halon-1301 CBrF3
Halon-2402 CBrF2-CBrF2
number
number
number
number
12.4
of
of
of
of
carbon atoms
fluorine atoms
chlorine atoms
bromine atoms
bromochlorodifluoromethane
bromotrifluoromethane
1,2-dibromo-1,1,2,2-tetrafluoroethane
[353-59-3]
[75-63-8]
[124-73-2]
How can I get the IUPAC chemical name from traditional names?
Alkane
Alcohol
Aldehyde
Acid
methane
form-
formic
ethane
acet-
acetic
n-propane
propion-
propionic
n-butane
n-butyr-
n-butyric
n-pentane
n-valer-
n-valeric
n-hexane
n-heptane
caprocaproic
enanth-
caproic
7
8a
n-octane
methanol
carbinol
ethyl
methyl carbinol
n-propyl
ethyl carbinol
n-butyl
propyl carbinol
n-amyl
butyl carbinol
hexyl
amyl carbinol
enanthyl
enanthic
hexyl carbinol
capryl
primary caprylic
heptyl carbinol
1-octanol
capryl
secondary caprylic
methyl hexyl carbinol
2-octanol
caprylcaprylic
caprylic
8b
enanthic
n-nonane
10
n-decane
12
n-dodecane
14
16
n-tetradecane
n-hexadecane
cetane
n-octadecane
n-eicosane
18
20
pelargonic
octyl carbinol
capric
nonyl carbinol
lauryl
lauric
myristyl
cetyl
pelargonic
pelargonic
caprcapric
laurlauryl
myristpalmit-
capric
stearyl
arachidyl
Primary
- alcohol
- amine
eg normal
R1CH2OH
R1NH2
straight chain
iso
branched chain
Secondary
- alcohol
- amine
eg
R1R2CHOH
R1R2NH
Tertiary
- alcohol
- amine
eg
R1R2R3COH
R1R2R3N
lauric
myristic
palmitic
stearic
arachidic
normal octane
normal butanol
iso-butane
iso-butanol
iso-octane
n-octane
1-butanol
2-methylpropane
2-methyl-1-propanol
2,2,4-trimethylpentane
sec-butanol
iso-propanol
2-butanol
2-propanol
tert-butanol
2-methyl-2-propanol
Chemists recognise that they should always number carbon chains from the
end with the functional group, so the location of double bonds in
unsaturated fatty acids are numbered from the carboxylic acid end, and
are usually designated by "delta" in their abbreviated names.
Biochemists are more interested in the actual role that chemicals play,
consequently they will consider the position from the end that is important.
In the case of natural fatty acids the double bonds are usually cis
configured, and it is the distance of the first double bond from the
terminal end of the carbon chain that is important. They use "omega" to
signify that the double bond is cis, and they are counting from the other
end. The great advantage is that chain length can be ignored, and compounds
that are subjected to the same biochemical processes are grouped together.
In 1967, the IUPAC/IUB commission responsible for lipid nomenclature
recommended that for unsaturated fatty acids with cis double bonds, that
the "omega" symbol be replaced with "n-x", where n = the length of the
carbon chain, and x is the distance from the terminal end.
Some examples:Common
Chemical
Chemical
Biochemical
Name
Name
Oleic
Elaidic
Ricinoleic
Linoleic
alpha Linolenic
gamma Linolenic
Arachidonic
EPA
Erucic
DHA
cis-9-octadecenoic
trans-9-octadecenoic
D-(+)-12-hydroxy-octadec-cis-9-enoic
cis-9,12-octadecadienoic
cis-9,12,15-octadecatrienoic
cis-6,9,12-octadecatrienoic
cis-5,8,11,14-eicosatetraenoic
cis-5,8,11,14,17-eicosapentaenoic
cis-13-docosenoic
cis-4,7,10,13,16,19-docosahexaenoic
d = delta
o = omega
c-C18:1d9
C18:1o9
t-C18:1d9
c-C18:1d9-12OH
c-C18:2d9
C18:2o6
c-C18:3d9
C18:3o3
c-C18:3d6
C18:3o6
c-C20:4d5
C20:4o6
c-C20:5d5
C20:5o3
c-C22:1d13
C22:1o9
c-C22:6d4
C22:6o3
EPA and DHA are widely known as the omega-3 fatty acids present in high
concentrations in marine lipids, and are considered beneficial in diet,
although research is not complete [4,5].
12.6
A Molar solution contains one gram molecular weight ( aka mole ) of the
reagent in one litre of solution, and is represented by " M ". In modern
usage, "molar" is intended to only mean " divided by amount of substance",
and is not supposed to be used to describe 1M solutions. There are already
exceptions to the rule ( molar conductivity, molar extinction coefficient ),
so I would only worry about correct usage in exams, as in the real world
Often the best place to start are MSDS sheets or catalogues from commercial
suppliers. Some textbooks include a list of named reagents and their
composition that are mentioned in the text. The very common reagents are
usually also detailed in Hawley or the Merck Index. One chemistry field that
has a lot of named reagents is analytical chemistry, especially in Thin Layer
Chromatography, where many of the spray detection reagents have common names.
Merck produces a handy guide describing the composition and production of
common TLC spray reagents [12].
Some common reagents include:- aqua regia = 1 part nitric acid and 3 or 4 parts hydrochloric acid.
- piranha solution = highly dangerous ( explodes on contact with traces of
organics ), warm (65C), 70:30 mixture of 100% sulfuric acid and 30%
hydrogen peroxide. It is used, with comprehensive safety precautions,
in the semiconductor industry, and also in some laboratories to clean
glassware [13,14,15]. Many chemical laboratories prohibit it, and there
are much safer, equally effective, alternatives available - refer
Section 16.7.
See the Merck Index for the chemical structure of your favourite poison.
Heilbron ( aka "Dictionary of Organic Compounds ), a multi-volume set,
is also excellent, and more up to date, though less commonly available.
Serious structure chasers should also check Beilstein, which often provides
far more detail of properties and structure than Merck or Heilbron.
13.4
Merck, Heilbron and Beilstein all provide information on drugs that have
a significant presence in the market. Lesser-known homebake and analogues
are usually not covered, and a search of Chemical Abstracts may not even
provide information. Because of the various techniques used to "refine"
and "cut" the active ingredients, most illegal drugs are seldom
sufficiently pure to match published data. The drugs are marketed on their
pharmacological and psychological activity, rather than chemical purity
- similar to vitamin units of activity :-). I suggest you start by reading
the various alt.drugs FAQs - they all list hardcopy references, and if they
do not identify an information source, try posting to alt.drugs or rec.drugs.
13.5
By asking the question in sci.chem, you already have signalled your level
of knowledge of illicit chemistry discussions on Usenet. You should be in
alt.drugs.* hierarchy and perhaps other groups in section 13.1 :-).
For the short answer, refer to Merck, Heilbron or Beilstein, they will
provide references to the original synthesis papers. Note that large scale
production techniques often use procedures that were developed later, and
street procedures often are significantly different, usually due to
financial, equipment, or chemical feedstock constraints.
For the long answers, see the "alt.drugs Clandestine Chemistry Primer/FAQ"
by Yogi Shan (yshan@nortel.ca), and visit some sites listed in the Network
Resources FAQ available in alt.drugs. For a fairly comprehensive overview,
( but no warranty implied for info available there ), you could start at:
http://hyperreal.com/drugs/
An interesting article on the link between methylenedioxymethamphetamine
( MDMA, ecstasy, XTC, Adam ) illegal synthesis and the sassafras tree is
available [1].
13.6
Well, if you do a lot of people will hate you. On the other hand many people
will love you. Of course, most people won't care one way or another.
Or maybe they'll just roll their eyes back, mumble something about
"dissipated/mis-spent youth", and hit the "next" button.
Posting them to sci.chem means you will be attempting to teach grandmother
how to suck eggs, most regulars of sci.chem *know* where to find the
complete instructions, how to perform the synthesis, and have authorised
access to all the equipment and chemicals. The readers of sci.chem are
probably not your target audience, and may be a little annoyed that you had
such a low opinion of their chemistry abilities. If you do not want a
lot of flames, try posting to the groups in section 13.1, they will probably
appreciate your contribution more, but will still flame you if it is wrong.
This is Usenet, do what you want as long as you think you can get away with
it. And don't ever let anyone tell you that you can't. It's a truism on
Usenet that whatever you do, someone's going to be mad at you. For every
anarchistic Free Spirit (TM), there's going to be at least one anal-retentive
busy-body who has nothing better to do that feign outrage at something or
other. Some idiot in Australia even had the nerve to flame me for posting my
Clandestine Chemistry FAQ to sci.chem, and I think drugs are terrible, and
said so. So go figure.
The only caveat to this is that posting mis-information, or information
that you personally do not understand, is likely to result in a lot of
flames. If you attempt to post anonymously to sci.chem, it is likely that
you will encounter far more opposition than if you use your email address.
As with all of Usenet, posters who sign their names to posts will be held
accountable for the content, so posting obviously incorrect or incomplete
syntheses to a group where knowledgeable chemists hang out is more likely to
harm your credibility. Your posts are unlikely to gain you further knowledge
of the synthesis, because if you post incorrect details, readers will be
pointed to the more accurate Clandestine Chemistry FAQ, and also directed to
the groups in section 13.1 to find the latest details.
In the late 1980s, and early 1990s a poster began to post all the detailed
synthesis methods from Pihkal to sci.chem. "Pihkal" is Alexander and Ann
Shulgin's standard text " Phenethylamines I Have Known and Loved [2a]", which
has recently been supplemented with "Tihkal" ( Tryptamines I have Known and
Loved ) [2b].
From vague memory, the poster was just listing the recipes, and not entering
into discussions or responding to questions or comments. There was the usual
outrage, but I believe he had to stop because of copyright violation of the
book he was posting - he could not demonstrate to his access provider that
he had approval from the copyright holder :-). Shulgin has now made Part Two
of PiKAL freely available, and copies are littered around the Internet, so
check out the various alt.drugs FAQs for their location.
13.7
Density
Heat of Combustion
Heat of Detonation
Gas Volume
Detonation Velocity
(g/cm3)
(MJ/KG)
(MJ/KG)
(cm3/g at STP)
(m/s)
Azide
4.0
2.64
1.54
308
5100
Fulminate
4.2
3.93
1.79
316
5400
1.60
13.58
3.43
876
6900
The advent of the WWW has meant that many educational institutions now have
their courses listed. A WWW search should reveal the address of most
institutions, and several of the more popular chemical courses are linked to
some of the general chemistry education sites listed in section 7.2.
Note that most US educational institutions will have a *.edu (education)
Internet address. Also check out the various Chemical Society homepages.
14.2
Once again, try using the WWW, as many educational institutions worldwide
are placing course information on their home pages. It is worth remembering
that not all countries use *.edu (education), as the educational institution
address, some countries use *.ac (academic) eg vuw.ac.nz is Victoria
University in Wellington, New Zealand.
Archive-name: sci/chem-faq/part4
Posting-Frequency: monthly
Last-modified: 22 October 1999
Version: 1.17
Subject: 15. Chemical Demonstrations
15.1
Yes. Good places to start are the four volume "Chemical Demonstrations"
by B.Z.Shakhashiri [1], the two volume "Chemical Demonstrations - A
Sourcebook for teachers" by Summerlin and Ealy [2], or "Chemical Magic"
by Ford and Grundmeier [2a]. The Journal of Chemical Education is also an
excellent on-going source of novel demonstrations and developments of
traditional demonstrations.
15.2
15.3
15.4
15.5
What
What
What
What
are
are
are
are
good
good
good
good
Growth time
1 hour
3 hours
5 hours
6 hours
~24 hours
~24 hours
~1 day
[ There have been several good discussions [4,5], and recipe compilations
[6], for many popular oscillating chemical reactions.]
A particularly dramatic 'trick' is not to burn paper. Make up a solution
containing 57% v/v ethanol and 43% v/v water with 5% w/w sodium
chloride. Soak a filter circle in the solution and hold it near a flame
(with tongs) just long enough to ignite. After the flames die down the
filter circle will still be intact. The ethanol burns but just enough
water remains in the paper to prevent ignition. NaCl is added to provide
a more convincing flame. To add drama, 'burn' a banknote - but ensure
that all of the note, especially the corners, is soaked.
From: lmartin@uclink.berkeley.edu (Lonnie C Martin) Date: 17 Feb 1993
Subj: Re: Growing a Silver Tree in Beaker?
In article <...> xslkkk@oryx.com (kenneth k konvicka) writes:
>Am trying to do a demo for elementary school kids. How do you grow a tree
>of silver using copper wire(?) submerged in a solution of AgNO3? Saw one
>in high school physics class about a thousand years ago at good ol' Reagan
>HS, Austin, Tx. Was really beautiful. The silver formed nice large
>plates. Any demonstration books you could steer me toward?
What you have described is about all there is to it. I do this
demonstration for the chemistry classes here at Berkeley about twice a
year, or so. Just make a "tree" out of copper wire (you might clean it
with sandpaper or steel wool) so that it will fit into a beaker of your
choice (we use 4 litre here), and pour in the silver nitrate solution.
I think we use 0.1 molar, but as long as the concentration is fairly close
to that, it will work just fine.
It is not necessary to make the tree very "bushy". The silver will fill it
out nicely with fuzzy thick hanging globs of crystals. The solution will
change from colourless to blue, as copper nitrate is formed. A very nice
experiment. You can expect this to take on the order of an hour to get
fully developed.
From: flatter@rose-hulman.edu (Neil Flatter)
Subj: Re: Need: A safe chemical display
VERY LONG
Date: 7 Jul 92
can, gently score around the circumference on the inside, (the inside is
coated to prevent a reaction between the soda and the can) and fill the can
with a solution of warm water and Copper(II)Chloride (CuCl2) so that the
solution is just above the score mark. Let this sit for a few minutes.
You are done with the solution when the outside of the can appears brownish
(blackish) where the score mark is. Gently pour out the solution (keep it)
and let the can sit. When ready, hold the top of the can in one hand and
the bottom in the other, and break like you are breaking a stick in half.
Two bits of advice :
BE CAREFUL!. You will end up with the sharp edge of the can, which can cut
severely!
Try this ahead of time just to make sure you get it right. Wait too long,
and when you pick up the can, it will split due to the weight of the
solution. Don't wait long enough and it won't work. My guess is about
5 minutes
P.S. This is more of a demonstration of structure of an aluminum can, but
if you want to demonstrate the "strength" before you rip it in half, place
the can on the floor, so it is sitting like it normally would, and balance
on one foot off the top of the can. It helps to have something nearby to
hold on to, and the can cannot have any dents. You would be surprised how
strong an empty can is. I weigh about 190 lbs, and have stood on an empty
soda can for 30 seconds, get off the can, and not have it collapse. This
takes some practice, so give it a try.
From: A_ROSATI@GUVAX.GEORGETOWN.EDU
<Anthony V. Rosati>
You can followup the bromophenol blue trick by brewing a cup of tea
and, while they watch, add some lemon juice. The color will lighten.
There is an indicator in tea that changes with the acidity of
ascorbic acid.
Another neat trick is to demonstrate the dehydration capacity of
concentrated sulfuric acid. Take a 500 mL beaker about one third full
of white table-sugar. Then add about a half-inch to one inches worth
of concentrated sulfuric acid. (This demonstration _MUST_ be conducted
in a hood) Let it sit for about five minutes. Within that time, the
sulfuric acid will seep in, start turning the color of the sugar
brown, and then black, followed by an intense, hot dehydration. The
sugar will start to form a jet black, smelly, sticky column that rises
out of the beaker. It is really impressive.....
You might want to also look up "oscillating reactions" in your
chemistry library. Many of these are simple to set up and generate
neat color cycles that would impress the kids!
From: mfrancis@ucsd.edu < Lyn Francisco >
1. Take a balloon, blow it up, tie it, then stick it in a vat of
liquid nitrogen. Wait until it shrinks (around 3 s or so), take it
out, and then watch it inflate in your hands. This will very nicely
illustrate the relation between temperature and pressure.
2. We did this during a demonstration to let the world know about
ACS on campus. Take a large container (like one of those 10-gallon
water containers, cut in half or something), fill it up with water,
then put in one can of the original Coke and one can of diet Coke.
Make sure that both cans are unopened. Now, drop a few pieces of
dry ice in the container. The original Coke should drop to the
bottom, and the diet Coke stay up toward the top. It was cool, and
attracted all the frat-types and non-science people to our table.
From: dfield@nike.calpoly.edu < Dan Field >
If you really want to fire them up, my favorite has always been the
hydrogen balloons. Just fill up several balloons, one color with air or
He, another with H2, and another with 2H2 + O2. You can fill them ahead of
time, or better yet if demonstration time allows, use the products of one
of your demonstration reactions to fill the balloons. Light a candle on
a L O N G stick, dim the lights, and pop!, boom!, B O O O M !!.
You'll have instantly created little monsters, young pyromaniacs virtually
guaranteed to associate some excitement with chemistry.
[ Warning - the sound level of such explosions has recently been found to
exceed health and safety guidelines, and people should read the article
before demonstrating this experiment to students or children [7]. ]
From: edremy@d31ha0.Stanford.edu < Eric R.>
There are lots of things you can do with liquid N2. Try freezing a
banana and using it as a hammer. (Follow by using an unfrozen banana:
kids love it!) Simply adding some to a test tube and (lightly!) corking
it is fun, provided you're careful with the cork. Shattering a
superball is also good.
However, my personal favorite for spectacular demos is the HCl fountain.
Ascii graphics follow
--------\
/
\
S
\
/
-|/ | \
/--|--\
/
|
\
-----------
Have them float through a bunsen burner flame suspended over the table and
they explode. VERY NEAT effect.
From: joec@morgan.com <Joe>
USUAL WARNINGS: many chemicals are poisonous and some reactions
may be difficult to control. Use your head.
Best done indoors
----------------Dissolve silver nitrate in warm water. Get some copper wire
and clean it with steel wool. Insert copper wire (preferably coiled
at one end) in the solution and it will immediately dull. Some time later,
silver crystals will be CLEARLY visibly growing on the copper.
The best effect is to let it sit overnight. The resulting
effect is downright beautiful
Dissolve Cobalt Chloride in warm water. Put some Aluminum foil
in it and watch it tarnish. Clean, polished Aluminum works
best but household aluminum foil also works (just slower).
The Aluminum slowly disappears and Cobalt metal shows up at the bottom.
This is a slow one but it does work.
Light an alcohol lamp, i.e. denatured alcohol and bring a magnet near
the flame but not above it- to the side. Watch the flame get pulled in
the direction of the magnet.
Sprinkle iron filings over the same alcohol lamp and watch sparks fly!
Ignite some Magnesium ribbon and drop into an atmosphere of CO2. It
will continue to burn with lots of noise and sparks. Carbon dust will
rain down as a byproduct.
Mix water and household (3 in 1) oil. Note the phase boundary.
Add soap and shake. Watch the phase boundary disappear.
Heat up a piece of blackboard chalk with a propane torch. Chalk
is CaCO3 - heating it up will drive off CO2, leaving CaO (also known
as lime). Heating up lime will cause the it to emit a whitish light,
which is where the phrase 'limelight' comes from.
[ Note - not all blackboard chalk is CaCO3 - test carefully first ]
Do these outdoors:
-----------------Get some KMnO4 and pour into a small pile. Depress the center of
the pile slightly and add a drop or two of Glycerine and stand back.
Something between 1-5 minutes later, it will burst into flame.
When it dies down, drop some more glycerine on it to have it flare up
again. Be careful disposing of the KMnO4 left over - its a powerful
oxidizer.
We also do THERMITE periodically (Aluminum powder and rust). Details for
those who ask - it burns *BRIGHT* and *HOT*.
Drop some dry ice chunks into a 2 liter PLASTIC soda bottle 1/2 full with
warm water which is then quickly sealed. Get at least 50' ft back rather
quickly. The pressure will build up and detonate with a LOUD *BOOM* after
a brief and unpredictable time. The bottle will break into many hundreds
of parts (don't use GLASS!) and you will get a mist cloud some 20-30'
across. Note: It is quite LOUD and may scare a younger audience.
Make Hydrogen soap bubbles and set them off. Get an erlenmeyer flask and
fit a cork into the top and route a glass tube through the tube and
have it bend down and into a jay of soapy water. Remove the cork and
drop in Zinc metal and pour in somewhat dilute HCl. Put the
cork back in and let the H2 bubble into the soapy water. This will
make H2 soap bubbles. Let them break free and ignite them with a light
match on long pole.
Thermite reaction
First of all....this is a fairly vigorous reaction so take the usual
precautions:
1-Do it outside, preferably on sand or dirt. Since it burns at 4000 degrees
fahrenheit, it will melt most anything. By the way, a nuclear explosion
burns at 8000 and the surface of our Sun burns at 10000. It will readily
melt rock salt, beach sand, etc. You get the idea.
2-It can spray sparks around. Keep it away from combustible materials. The
burning sparks are either molten Aluminum or molten Iron.
3-It is VERY bright so you shouldn't stare at it.
4-It puts out lots of smoke.
Here is how I do it.
Ingredients:
1-Aluminum powder
2-Iron Rust (Red-Fe2O3).
Grind carefully and separately into a powder-like consistency.
Mix in roughly equal proportions, by volume with an excess of rust.
Mix thoroughly to get an even color.
Pour the powder mixture on the ground in a pile.
Get magnesium ribbon and lay it on top of the pile, and press partially
into the pile. Do not smother the Mg ribbon. Ignite the ribbon with a
propane torch and get back quickly.
When done, be careful...it will leave molten, glowing red iron as a
byproduct.
You can make rust by mixing household clorox with steel wool pads and let
sit overnight and then filtering out the rust.
Have fun and be careful.
Usual disclaimers apply
From: gallivan@after.math.uiuc.edu < Justin Gallivan >
This works nicely with soap bubbles in a dish. If you have the H2 and O2
tanks available, Try a few with the H2 only which makes a nice quiet
flame and add the O2 later for a little shock value. You may want to
try this first for safety's sake but it always went off without a hitch in
my general chemistry days.
From: Rob
I hope I'm not too late. An extremely simple trick is done with a chunk
of styrofoam (larger the better) and some acetone, which is an excellent
theta-solvent for styrofoam.
Simply spray the acetone out of a bottle onto the styrofoam, and the
styrofoam rapidly decomposes, losing its structure, and appears to
actually be melting. It is quite a "dramatic" demonstration, and can be
offset against how nicely styrofoam coffee cups hold water/coffee, but not
acetone.
From: ?
I thought this one was neat...
Take a bottle (should be reasonable size, like a ketchup bottle)
fill it to within 2" of the top, color light blue (not opaque!)
with methylene blue. Drop in a NaOH pellet and a few drops of
Karo clear syrup. Other reducing sugars might work; I just know
it works with this syrup. (Or did; the last time I tried it was
almost 20 years ago, and they may have changed the formula since
then.)
Over a period of a few minutes, the blue color will fade. Shake
the bottle, and suddenly it's blue again. Leave it, and it will
slowly fade. It'll last for a couple of days, until random
microbes do in the sugar I suppose.
From: ?
A "Bottle of fire" for lighting bunsen burners and such:
Get a dark, heat-resistant glass bottle, and put just enough pentane
in it to wet the sides. (i.e., rinse it with pentane and dump out
the excess.) Light the top of the bottle. The flame will burn down
into the neck of the bottle a little, but be almost invisible to the
audience. Pick up the bottle, turn it over, and flames will pour
out. Set it down, and the flames seem to go out.
When Dr. Toffel did this, someone said "There's something in the
bottle!" He said "Nope," poured some water from the faucet into the
bottle, dumped fire and water into the sink, then showed that the
bottle would still "pour fire". (This probably takes some practice.)
From: mvp@hsv3.lsil.com < Mike Van Pelt >
Portable bunsen burner:
Bubble air through a test tube of pentane, and run this to
your bunsen burner. You can use a large balloon as your air source,
or have a vict... I mean, volunteer, blow through the tube.
From: Howard Clase.
One experiment that I
which is clear, and a
which is also clear.
a yellow solid - lead
On
mirror effect. Other reducing metals can be used, such as iron, but I
haven't tried these myself.
From: ?
Grind some potassium permanganate to a fine powder (to speed up the
reaction). Put it in a small heap (1 teaspoon) on a tile, make a dent in
the top and pour one drop of glycerine in the hole. After about 10-15
seconds the heap will catch fire.
From: torin.walker@rose.com
Here are some that are rather interesting. All of these tests have been
performed in my workshop and are all safe (with the exception of the
handling of HCl and the irritating effect of experiment #2). Experiment #3
is by far the most fascinating.
1 Copper Sulfate couple grams in a test tube.
Sodium Bicarbonate - same as above.
These two liquids are transparent but when mixed, turn into a soft blue
opaque suspension.
2 Glycerin and HCl
Takes a long time (couple of hours) to complete but when these two clear
liquids are mixed together, it turns from clear to a deep transparent red
and slowly goes brown. Warning - this is extremely irritating to the eyes
if you are exposed to it for a while - usually, an hour is enough to
really get you annoyed.
3 (My favorite) Acetone (you can buy large tins of this stuff (1L) at a
hardware store in the automotive section (usually with the bondo and
other body repair supplies) and styrofoam (a large bag of popcorn type
packaging filler will be needed.)
When styrofoam is placed in acetone, the styrofoam ( large volume of
styrofoam for a small volume of acetone ) dissolves and becomes a wet,
play-dough like substance that feels cold to the touch.
This experiment is harmless unless swallowed :-) and should prove to be
quite interesting to the students.
The coldness is due to the evaporation of the acetone from your skin
(ever use nail polish remover? That's acetone.) The acetone will
eventually all evaporate (a 2 inch sphere of this will take a day or two)
and the result will be a porous (trapped acetone bubbles) material that
can be molded to any shape you wish.
From; David O'Driscoll. University of Central Queensland...
Hope someone hasn't already done this one, I have been studying for
exams so have not been reading all of them.
The one we use at our high school demos are pH clocks....
quite good as they are not static displays.
First, take three or four large (1L) beakers and 3/4 fill them then
take your favourite pH indicators (ones with good colours), and add a
few drops to them, then add some dilute sodium hydroxide or something
to make them slightly basic. Next add a handful of dry ice to each beaker.
This creates a nice bubbling mixture with good visual effects, what happens
is obvious (I hope!!!). Some of the CO2 is dissolved in the water, turning
the mixture acidic and when the end-point of the indicator is reached the
colour changes - sometimes quite dramatically. The kids seem to like it and
the chemistry is not too involved.
From:webbb@mbf.UUCP ( Bryan Webb )
I didn't see the originating message of this thread, but from the
responses that have made it here, I think this is the kind of stuff
you might be looking for. In earlier times, I've done these:
1) Place a small pile (several grams) of powdered magnesium on a surface
you don't care about in an environment provided with plenty of
ventilation. On top of this, place a couple of grams of powdered
iodine (well, as close as you can get to it, though that might not
be crucial). Now, put a couple drops of water on the iodine ...
enough to also contact the magnesium ... and stand back. The heat
of the reaction vaporizes some of the remaining iodine into a purple
vapor.
2) This is pretty dangerous, so be very careful. Take a couple of grams
of red phosphorous and place on top of a couple of grams of potassium
iodate. Rapidly stand back... spontaneous combustion. My experience
was a time delay of a couple of seconds, but I wouldn't want to count
on it... I discovered this accidentally... boy was I surprised. The
speed of the reaction may be related to the humidity.
3) Potassium dichromate is normally bright orange at room temperatures.
it is cooled to liquid nitrogen temperatures, it becomes yellow. If
heated, it becomes a deeper red color. I'm not aware of any other
inorganics that have this range of color change when the temperature
is varied.
4) Ahhh, my favorite... When I was in high school, I took the 2nd year
chemistry class that was offered. We had the resources of the
school at our disposal, so long as the experiment we wanted to do
was "in a book". The book I had was "Chemistry Magic", and described
an "experiment" where some cotton balls were placed on a fireproof
surface, a few grams of Sodium Peroxide was placed on top, and then
you put a drop or two of water that will wet at least a little bit
of both the peroxide and the cotton.
If
forms explosive mixtures with many organics. IF you still want to try
it, immerse the tube in the nitrogen and then immediately run the gas
in. only do a little bit. How much you get depends on what proportion
of weights of low hydrocarbons the gas contains ( I think methane
condenses at this temp, but not quantitatively like some stuff, unless
there is a large surface area)."
6) One of my classmates made luciferin [sic]. It's a liquid that
glows in the dark for about 12 hours. That was fun too!
Happy researching!
Standard disclaimers apply; I'm not sure my company would have hired
me if they had the foregoing admissions before them.
Non-standard disclaimers too: I don't recommend you do any of these things
either.
From: fred@theory.chem.pitt.edu < fred >
If you would like to condense out methane gas in a relatively safe way,
fill a balloon with the gas and THEN condense the gas with liquid N2.
You can use scissors to cut the balloon, and pour the liquid CH4 into
a beaker with water in it (notice that it floats, forms ice, etc.) and
light it. Only the fumes burn as they mix with atmospheric oxygen.
This makes a fair "olympic torch." Wear goggles etc.
From: Larry (Call me "Lefty") C
One that can be safely performed with a long enough spatula.
Mix Calcium Carbide with any strong oxidizer (KMnO4, NaNO3, even MnO2
works). Proportions aren't real important here.
Using face shield, gloves, lab coat and long spatula, drop a SMALL
amount (say, 1 gram or so) of this into common household bleach.
Acetylene and chlorine are evolved, which immediately, uh... exploded
Delightful chlorinated hydrocarbons result, unfortunately :(
15.6
" Slime " is a trademarked commodity obtained by cross-linking guar gum and
borax, and is marketed by the Mattel Toy Corporation. The slime produced for
demonstrations is usually made by cross-linking a poly vinyl alcohol (PVA)
product using borate. The normal method is to carefully prepare a 4%
mass/volume aqueous solution of a hydrolysed high molecular weight PVA
( >100,000 ) - available from Eastman Kodak. Commercial PVA-based adhesives
( such as Elmer's Glue ) will also produce a reasonable quality slime, as
will polymeric materials that have multiple hydroxyl groups and can form
highly-hydrated gels, such as guar gum - but some experimentation may be
required to ascertain optimum ratios.
2H2O
<==>
(B(OH)4)-
H3O+
pK = 9.2
The borate ion is tetrafunctional when interacting with the alcohol groups
of polyols, and thus builds the cross-linking structure. PVA has about 1-2%
of 1,2 diols amongst the remaining 98-99% of 1,3 diols. To obtain the desired
properties, the bonds between the borate and the PVA must be weak, and it is
believed they are hydrogen bonds ( shown as ... below ).
PVA
Borate
H
|
O-H...O
PVA
H
|
O-H...O
\ /
\
/
\ /
H-C
\
/
C-H
/
B\
CH2
/
\
CH2
\
/
\
/
H-C-O...H-O
O...H-O-C-H
/ |
|
\
H
H
Although individual hydrogen bonds are weak, the large number of available
OH groups in highly-hydrolysed PVA will result in a hydrated, 3-dimensional,
gel, rather than a borate precipitate. The continual breaking and reforming
of the bonds under low mechanical stress, and the large amount of water
incorporated into the gel, are responsible for the rheological properties of
the hydrated gel. Slime can be broken down by reducing the concentration of
borate by titration with a strong acid, and details of such a procedure have
been recently published [12].
What are the best drying agents for liquids and gases?
Many older laboratory texts insist that volumetric glassware should not
be oven dried because of the danger of irreversible and unpredictable
volume changes. However most modern laboratory glassware is now made of
Pyrex, and work by D.R.Burfield has demonstrated that low temperature
drying does not significantly affect the calibration of volumetric
glassware [10]. He demonstrated that exposing volumetric flasks and
pipettes to 320C, either continuously or thermally cycled, resulted in no
significant detectable change to the calibration. He concluded that
"oven temperatures in the range of 110-150C should provide efficient drying
of glassware with no risk of discernible volume changes, even after
prolonged use, providing that Pyrex glass is the material of construction".
16.3
In 1935 Karl Fischer used the reaction between iodine, sulfur dioxide, and
water to produce a technique for quantifying water [11]. In aqueous solution,
the reaction can be presented as I2 + SO2 + 2H2O <=> 2HI + H2SO4.
He used anhydrous methanol to dissolve the I2 and SO2, and added pyridine
to move the equilibrium to the right by reacting the acidic products.
Fischer assumed his modifications did not change the reaction and one mole of
iodine was equivalent to two moles of water. Smith et al.[12], demonstrated
that both the methanol and pyridine participate in the reaction and one mole
of iodine is equivalent to one mole of water. They suggested two steps:(1) SO2 + I2 + H2O + 3RN -> 2RN.HI + RN(SO2)O
(2) RN(SO2)0 + CH3OH -> RN(SO4CH3)H
(where R = base = C5H5 for pyridine)
This was further investigated by E.Scholz [13], who proposed:
(1) CH3OH + SO2 + RN -> (RNH)SO3CH3
(2) H20 + I2 + (RNH)SO3CH3 + 2RN -> (RNH)SO4CH3 + 2(RNH)I
(where R = Base)
The advantage of the Karl Fischer titration is that it has few interferences
and can quantify water from < 1ppm to 100% in diverse samples, ranging from
gases to polymers. It will measure all water that is made available to the
reagent. the endpoint is usually ascertained using a dead-stop endpoint,
and for low water levels coulometric techniques are used to quantitatively
produce the iodine by anodic oxidation of iodide. The procedures are
described in detail in ASTM, AOAC etc.
16.4
The Dean and Stark procedure can be used to measure the water content of
a diverse range of samples, and has been extensively used in industrial
laboratories to measure water in petroleum oils. The technique can measure
% levels of water, but is not as accurate as the Karl Fischer titration,
and is not applicable to samples where the water is not liberated by the
solvent. The sample is mixed with a solvent ( usually a toluene/xylene mix )
and refluxed under a condenser using a special receiver. There are two common
designs of receivers, one for solvents that are heavier than water, and the
more common one for solvents that are lighter than water - illustrations will
be shown in most laboratory glassware supplier catalogues.
The water and solvent are refluxed, and as they condense the two phases
separate as they run into the receiver. The water remains in the receiver
while the solvent returns to the flask. The Dean and Stark technique is also
useful for removing unwanted water from reactions, eg the synthesis of
dibutyl ether by the elimination of water from two molecules of n-butanol
using acidic conditions. An example of this is provided in the preparation
of dibutyl ether described in Vogel, and detailed procedures for the
determination of water using Dean and Stark are provided in ASTM and AOAC.
16.5
The soxhlet extractor enables solids to be extracted with fresh warm solvent
that does not contain the extract. This can dramatically increase the
extraction rate, as the sample is contacting fresh warm solvent. The sample
is placed inside a cellulose or ceramic thimble and placed in the extractor.
The extractor is connected to a flask containing the extraction solvent, and
a condenser is connected above the extractor. The solvent is boiled, and the
standard extractor has a bypass arm that the vapour passes through to reach
the condenser, where it condenses and drips onto the sample in the thimble.
Once the solvent reaches the top of the siphon arm, the solvent and extract
are siphoned back into the lower flask. The solvent reboils, and the cycle
is repeated until the sample is completely extracted, and the extract is
in the lower flask.
There is an alternative design where the hot solvent vapour passes around
the thimble, thus boiling the solvent in the thimble - this can be a problem
if low-boiling azeotropes form. Procedures for using soxhlet extractors are
described ( along with illustrations which might make the above description
comprehensible :-) ), in Vogel and many other introductory organic laboratory
texts.
16.7
involve the use of hazardous and corrosive chemicals, and details of the
necessary safety precautions for each cleaning solution should obtained
before attempting to clean glassware. The use of heat and/or ultrasonic
agitation can greatly improve the removal rate of many deposits, especially
inorganic and crystalline deposits.
Whilst the semiconductor industry use piranha solution ( refer Section
12.9 ), and several other reactive and toxic chemicals for cleaning, those
reagents can react dangerously with the residues found in laboratories, and
their use is prohibited in some institutions. Such chemicals should only be
used after extensive prior consultation with laboratory management and safety
staff - to either identify safer alternatives, or to ensure that appropriate
protective and safety systems are in place.
If the probable composition of material deposited on the glassware is known,
then the most appropriate cleaning agent can be readily selected. There are
several safe aqueous cleaning solutions that are routinely used. If possible,
glassware should be washed or soaked immediately with an appropriate solvent
for the residue. This will make subsequent cleaning easier, but all traces
organic solvents must be removed before using any cleaning solution.
The most common aqueous-based soaking solutions are commercial formulations
that usually contain alkalis, chelating agents, and/or surfactants, and can
be used either at ambient temperature, or temperatures up to boiling ( with
ventilation - caustic fumes are noxious ). These are very effective for
general grime, most labels, pyrogens, and many common chemical residues, and
well known examples include RBS-35, Decon, Alconox, and Pyroneg. Their main
advantages are low toxicity and ease of disposal.
The next common strategy involves physical abrasion to remove deposits
inside flasks, usually with a bottle brush and an aqueous cleaning solvent
( like those above ) or a suitable organic solvent. A refinement is to add
sand, pumice, glass spheres, or walnut shell chips, along with some water
or solvent, and shake vigorously. It's important that the sand should not
have sharp edges - as it can scratch the glass. It has been suggested that
table salt in solvent ( eg petroleum spirit, methylene chloride, acetone )
is superior, as it doesn't scratch the glass, can be easily removed by
washing with water, and has minimal disposal problems [14].
The traditional glassware cleaning solution is "chromic acid", and many
analytical chemistry texts detail the preparation [15,16]. Chromium (VI) is
highly toxic ( mutagenic, carcinogenic ), and disposal is expensive, as all
solutions containing more than 5 mg/l of chromium are considered hazardous
waste in the USA. Disposal of chromic acid requires a two-stage process,
involving bisulfite addition to reduce Cr(VI) to Cr(III), followed by
neutralisation of the acid. There have also been several reports of
spontaneous explosions of chromic acid cleaning solutions [17,18,19],
consequently the use of chromic acid for cleaning glassware is declining,
and several alternative glassware cleaners have recently been evaluated [20].
Sodium dichromate dihydrate is usually used to prepare chromic acid, as
potassium dichromate is less soluble in sulfuric acid. One technique is to
dissolve 140g of technical grade sodium dichromate dihydrate in approximately
100 ml of water. Add two litres of technical grade 98% sulfuric acid to a 4-5
litre glass beaker that is sitting in a cold water bath in a fume cupboard.
Carefully stir the acid gently and pour a few mls of the dichromate solution
slowly into the acid. Keep repeating the addition every few seconds - after
the previous dose has been dispersed. As long as the stirring is gentle and
continuous, little or no splattering should occur, but the solution will
become quite warm. Allow to cool before storing in a glass-stoppered reagent
bottle. Always ensure that the stopper is sufficiently loose to release any
The standard text for common processes remains Shreve, and I must admit that
I enjoy reading the 1945 first edition to obtain a good overview of an
industry. McKetta provides excellent process design details, along with
comparisons of various processes. Kirk Othmer provides an excellent update
on the various processes and chemicals used extensively today. Kirk Othmer
remains the first port of call, but Ullmann is a close second. Both of these
provide extensive references to more specific texts.
Industry journals, eg Hydrocarbon Processing, offer annual reviews of the
processes used in their industry. Patent literature has to be treated
cautiously, as it is not always immediately obvious which patents detail
actual viable processes. Chemical engineering texts, eg Perry, provide
comprehensive detail of the equipment and operational parameters.
2)
(Ph)-O-CO-CO-O-OH
3)
C2O4 + Dye
4)
-->
O-O
| |
OC-CO
(Ph)-OH
Most of the desirable food aromas come from low to medium molecular weight
organic compounds - usually alcohols, aldehydes, esters, ketones, and
lactones. These may be " natural " ( extracted from natural sources ),
" nature-identical " ( synthetic, but identical to known natural compounds ),
and " artificial " ( synthetic, not found in nature ). The perceived aroma of
molecules can change dramatically with minor isomeric or structural changes,
and common fruity aromas are usually complex mixtures of several compounds.
Because man-made chemicals are frequently made from chemicals derived from
fossil fuels, the isotopic ratios of the carbon atoms has been used to
discriminate between natural and nature-identical chemicals. Natural
processes usually involve the use of enzymes that selectively produce a
specific isomer, and some man-made aromas are now produced enzymatically.
Chiral chemistry, often utilising chiral chromatography that was initially
developed for pharmaceuticals, is now also being used for the production
and testing of man-made aromas, as enantiomerically-pure aroma chemicals
command premium prices.
Some chemicals are listed below, along with their use in either fragrances
and/or flavours, and boiling point ( 760 mmHg, unless otherwise stated ).
Some of them are also considered toxic, and thus their use may be controlled.
Volume A11 of Ullmann has an excellent monograph on flavours and fragrances,
and more detail can be obtained from the journal Perfumer and Flavorist.
The catalogues of well-known suppliers such as Dragoco GmbH ( Germany ),
L.Givaudin and Cie ( Switzerland ), and Takasago Perfumery Company ( Japan ),
also contain information on chemical composition and health and safety.
Chemical
acetoin
acetophenone
benzyl acetate
butyl acetate
2,3-butanedione
(+)-carvone
(-)-carvone
citral
citronellal
BP
CAS RN
C (mmHg)
148
[513-86-0]
202
[98-86-2]
206
[140-11-4]
125
[123-86-4]
88
[431-03-8]
230
[2244-16-8]
230
[6485-40-1]
229
[5392-40-5]
207
[2385-77-5]
Application
butter
orange blossom
jasmine
apple
butter
caraway, dill
spearmint
lemon
balm mint
decanal
208
[112-31-2]
dihydromyrcenol
78 (1) [18479-58-8]
2,6-dimethyl-2-heptanol
171
[13254-34-7]
ethyl butyrate
120
[105-54-4]
ethyl 2t-4c-decadienoate
71 (45) [3025-30-7]
ethyl hexanoate
168
[123-66-0]
ethyl isovalerate
132
[108-64-4]
ethyl 2-methylbutyrate
133
[7452-79-1]
geraniol
229
[1066-24-1]
hexyl acetate
169
[142-92-7]
hexyl salicylate
168 (12) [6259-76-3]
1-(4-hydroxyphenyl)-3-butanone
[5471-51-2]
isoamyl acetate
143
[123-92-2]
(+)-limonene
176
[5989-27-5]
linalool
198
[78-70-6]
linalyl acetate
220
[115-95-7]
8-mercapto-p-menthan-3-one
57 (8) [38462-22-5]
1-p-methene-8-thiol
40 (1) [71159-90-5]
3-methyl-2-cyclopenten-2-ol-1-one
[80-71-7]
4-methyl-2(2-methyl-1-propenyl)tetrahydropyran
70 (12) [16490-43-1]
myrcenol
78 (50) [543-39-5]
2t-6c-nonadien-1-ol
98 (11) [28069-72-9]
3-octanol
175
[20296-29-1]
1-octen-3-ol
84 (25) [3391-86-4]
phenethyl acetate
238
[103-45-7]
phenethyl alcohol
220
[60-12-8]
phenethyl isoamyl ether
[56011-02-0]
2-propenyl hexanoate
alpha-pinene
156
[80-56-8]
alpha-terpineol
217
[98-55-5]
alpha-trichloromethylbenzyl acetate
[90-17-5]
18.4
citrus
lavender
freesia
pineapple
pear
pineapple
blueberry
apple
roselike
pear
azalea
raspberry
banana
lemon
lily of the valley
bergamot
blackcurrant
grapefruit
caramel
rose
lime
violet
mushroom
mushroom
rose
rose
chamomile
pineapple
pine
lilac
rose
Aside from thinking about your stomach, when the smell of cooking foods
is attractive, then most people like the smell of flowers and citrus fruits.
These are volatile, aromatic, oils, whose major components are complex
mixtures of medium volatility compounds, often derived from terpenes, eg
Oil of Rose ( 70 - 75% geraniol = (E)-3,7-dimethyl-2,6-octadiene-1-ol ),
Oil of Bergamot ( 36 - 45% linalyl acetate = 3,7-dimethyl-1,6-octadien-3-yl
acetate ). Many aromatic oils are mixtures of terpene esters ( oil of
geranium = 20 - 35% geraniol esters ) or aldehydes ( oil of lemon grass =
75 - 85% citral = 3,7-dimethyl-2,6-octadienal ). Merck briefly describes
nearly 100 volatile oils, from Oil of Amber to Oil of Yarrow, along with
typical applications. Flower perfumes are complex blends of compounds, and
detailed compositions of your favourite smell are often available in the
journal " Perfumer and Flavorist ".
Expensive flower petal perfumes, such as rose and jasmine, are produced
using extracts obtained by the traditional "enfleurage" process ( refer to
Section 24.4 ).
Relative Sweetness
0.46
0.68
0.84
1
30
200
300
650
2,000
3,000
160,000
200,000
200,000
220,000
Category
Natural Food Product
"
"
"
"
"
"
"
"
"
EC Permitted, USA Prohibited
EC, USA Permitted.
EC Permitted, USA Prohibited
Au, Ca Permitted, trials elsewhere
Undergoing trials
EC permitted, US chewing gum only.
Guanidine sweetener
"
"
"
"
"
"
The guanidine sweeteners are not expected to be approved for food use.
There are several other important attributes of sweeteners, such as
low toxicity, no after-taste, whether metabolised or excreted, etc.,
that must also be considered.
The potency scale is fairly flexible, and differing publications can
assign different values. The August 1995 copy of the Journal of Chemical
Education contained several papers from a symposium on sweeteners [3,4],
Both Vogel ( qualitative inorganic ) and the Rubber Handbook list details of
flame tests for elements. The spectra of the alkaline earth compounds are
relatively complex, so using filters to view the flame can change the colour
observed as dominant lines are filtered out. In general, except for copper,
any compound of an element can be used, however toxic salts ( such as
cyanides ) should not be used. Halogen salts are usually readily available,
and are reasonably volatile. In all cases, perform experiments in a
well-ventilated area - preferably a fume hood. The emission spectra in the
visible region is the sum of several emission lines, with dominant lines
masking others. The visible spectrum is approximately :Red
800 - 620 nm
Orange
620 - 600 nm
Yellow
600 - 585 nm
Green
585 - 505 nm
Blue
505 - 445 nm
Violet
445 - 400 nm
There are also the various bead tests employing borax ( sodium tetraborate
Na2B4O7.10H2O ), Microcosmic salt ( NaNH4HPO4 ), or sodium carbonate
(Na2CO3), using both oxidising and reducing flames. The bead test procedures
are detailed in Vogel ( qualitative inorganic ), and similar texts.
Element
Colour
Arsenic
Light Blue
449.4 nm, 450.7 nm.
( Arsenic is highly toxic - only perform in fume hood under supervision )
Barium
Green-Yellow
553.6 nm, 539.1 nm, 536.1nm, 614.2 nm.
Blue (faint)
455.4 nm, 493.4 nm.
Cesium
Red-Violet
852.1 nm.
Calcium
Orange
618.2 nm, 620.3 nm.
Yellow-Green
530.7 nm, 559.5 nm.
Violet (faint) 422.7 nm.
Greenish with blue glass.
Copper
Emerald Green
521.8 nm, 529.2 nm, 515.3 nm.
Not chloride, or in presence of HCl
Azure Blue
465.1 nm.
Copper chloride, or HCl present
Lead
Light Blue
500.5 nm.
( Lead is highly toxic - only perform in fume hood under supervision )
Lithium
Carmine Red
670.78 nm, 670.79 nm.
Orange (faint) 610.1 nm.
Violet with blue glass
Potassium
Red
766.5 nm, 769.9 nm.
Violet
404.4 nm, 404.7 nm.
Violet
Yellow
Impressive coloured flames have been obtained using chlorides and a methanol
flame in a petri dish [6]. Even more spectacular results have been obtained
by nitrating cellulose filter paper, and impregnating it with salts prior
to ignition [7].
18.9
).
n-decane
n-dodecane
n-tetradecane
19.3
46
74
99
210
204
200
0.75
0.60
0.50
5.6
-
Critical
Pressure
( bar )
112.8
73.75
41.25
52.7
49.1
49.90
36.62
29.8
40.57
83.1
72.54
42.66
227.1
58.38
Density
(g cm^-3)
0.235
0.468
0.558
0.271
0.212
0.524
0.550
0.608
0.508
0.453
0.225
1.105
=
=
=
=
=
=
=
=
After inserting the expressions for the surface area of a sphere (r = radius)
and number of moles, and differentiating, then we obtain:r(mininum) = 2 * gamma / ( P * ln(C/Cs))
This describes the size of a bubble that would continue to grow under the
existing conditions, rather than redissolve. Of course, the expression
assumes homogeneous precipitation of the bubble, and in real life most
bubbles are created heterogeneously. Statistics and kinetics are also
required to determine the rate of formation of bubbles, and predict the
effect of changing parameters such as temperature. As the liquid is warmed,
bubbles may be created faster, as the higher temperatures overcome the
activation barrier - which is the difference between the Gibbs free energy
when r is less than r(minimum), and the Gibbs free energy at r(minimum).
The formation of a bubble also dramatically perturbs the system, even
causing secondary bubbles to form. Secondary bubble formation may be
implicated in the production of copious quantities of froth from shaken,
quickly-opened, carbonated drink containers. The sites for gaseous bubble
formation in supersaturated drinks are typically small particles, or minor
flaws on the smooth surface of the container.
19.5
First, let's look at the melting points of some of the elements surrounding
mercury in the periodic table ( in degrees C ) :Period
IB
IIB
IIIA
4s3d4p
Cu 1083
Zn 419.5
Ga
29.8
5s4d5p
Ag
960.8
Cd 320.9
In 157
6s(4f)5d6p
Au 1063
Hg -38.4
Tl 304
The interesting comparison is between Hg and Au, as their properties differ
dramatically, although their electron structures are similar:14
10
1
Au(g) :
Xe | 4f , 5d , 6s
79
54
14
10
2
Hg(g) :
Xe | 4f , 5d , 6s
80
54
Very few chemistry textbooks discuss relativistic effects on chemical
properties, despite the availability of a comprehensive review by P.Pyykko
[12]. There several good introductory articles on the derivation and
calculation of various relativistic effects in molecules and atoms, so I'm
not going to include details [13,14,15]. Suffice to say, that whilst
smaller elements can treated simply, larger elements need treatment based
on the Dirac equation, which shows that the s electrons are approaching
the speed of light, consequently relativistic effects are important.
If we take the relativistic mass of mercury (m);-
Mo
-------------------_____________
/
( v ) 2
/ 1 - ( - )
\/
( c )
where
c (speed of light) = ~137 atomic units
v = Z = 80
Mo = rest mass
When light passes between media of different density, the direction of the
beam is changed as it passes through the surface, and this is called
refraction. In the first medium, the angle between the light ray and the
perpendicular is called the angle of incidence (i), and the corresponding
angle in the second medium is called the angle of refraction (r). The
ratio sine i / sine r is called the index of refraction, and usually the
assumption is that the light is travelling from the less dense (air) to more
dense, giving an index of refraction that is greater than 1. Although the
theoretical reference is a vacuum, air ( 0.03% different ) is usually used.
The refractive index of a compound decreases with increasing wavelength
( dispersion ), except where absorption occurs, thus the wavelength should
be reported. The D lines of sodium are commonly used.
The refractive index of a liquid varies with temperature and pressure, but
the specific refraction ( Lorentz and Lorentz equation ) does not. The molar
refraction is the specific refraction multiplied by the molecular weight,
and is approximately an additive property of the groups or elements
comprising the compound. Tables of atomic refractions are available in the
literature, as are descriptions of the common types of refractometers [1].
20.2
power challenge machines. These are all running Irix, which is SGI's
adaptation of Unix. SGI is popular for two reasons; first that the power
is very good for the price, second that SGIs run the largest range
of chemical software. However, you will find some computational chemistry
software that can run on almost any machine.
As far as graphics quality, the SGI Onyx (about $250,000) is about
the top of the line. Even if you find a machine that claims to have better
graphics than this, chances are you won't find and chemistry software that
can utilise it.
For chemical calculations there is no limit to the computing
power necessary. There are some calculations that can only be done
on the biggest Crays or massively-parallel machines in the world. There
are also many calculations which are too difficult for any existing
machine and will just have to wait a few years or a few centuries.
21.2
21.4
Internet: info@softshell.com
http://www.softshell.com
lamp ) also means that purified samples can be scraped off the plate and
be analysed by other techniques. There are special plates for such
preparative separations, and there are also high-performance plates that can
approach HPLC resolution. The technique is described in detail in Stahl [2]
and Kirchner [3].
23.3
Ion chromatography has become the method of choice for measuring anions
( eg Cl-, SO4=, NO3- ) in aqueous solutions. It is effectively a development
from ion-exchange systems ( which were extensively developed to deionise
water and soften aqueous process streams ), and brings them down to HPLC
size. IC uses pellicular polymeric resins that are compatible with a wide pH
range. The sample is eluted through an ion-exchange column using a dilute
sodium hydroxide solution. The eluant is passed through self-regenerating
suppressors that neutralise eluant conductance, ensuring electrochemical
Capillary electrophoresis uses a small fused silica capillary that has been
coated with a hydrophilic or hydrophobic phase to separate biomolecules,
pharmaceuticals and small inorganic ions. A voltage is applied and the
analytes migrate and separate according to their charge under the specific
pH conditions, as also happens for electrophoresis. The capillary can also
be used for isoelectric focusing of proteins. The use of salt or vacuum
mobilisation is no longer required.
23.9
0
0.0098
0.0214
0.0230
0.047
0.054
1.676
10
0.0091
0.0195
0.0185
0.037
0.041
1.163
20
0.0086
0.0182
0.0152
0.030
0.032
0.848
30
0.0084
0.0170
0.0133
0.026
0.028
0.652
40
0.0084
0.0164
0.0119
0.022
0.025
0.518
50
0.0086
0.0161
0.0108
0.020
0.024
0.424
60
0.0090
0.0160
0.0100
0.019
0.023
0.360
I've no explanation for the aberrant trend for helium at higher temperatures,
but I assume it's real - but it's irrelevant for HPLC solvents that are
usually stored at ambient temperature. Points to note - the lower solubility
of helium over the range of concern, *and* the lower rate of change of
decreasing solubility with increasing temperature. There is heat generated
in the compression of the solvent, along with friction in HPLC pump heads
and, more importantly, HPLC columns are often heated - thus the solvent
could outgas and form bubbles in UV detector cells that are at ambient.
By using helium, there is less chance of that happening. For example, if the
temperature increased from 10C to 40C, the undissolved gas volume would be
0.0007 cm3 for helium, and 0.0066 cm3 for nitrogen.
Modern HPLCs are sold with a "solvent degassing module" that removes
undissolved gases in the solvent automatically. These usually consist of
a tube made from gas-permeable membrane that passes through a vacuum
chamber.
23.10
There are four major intermolecular interactions between sample and solvent
molecules in liquid chromatography, dispersion, dipole, hydrogen-bonding,
and dielectric. Dispersion interactions are the attraction between each pair
of adjacent molecules, and are stronger for sample and solvent molecules
with large refractive indices. Strong dipole interactions occur when both
sample and solvent have permanent dipole moments that are aligned. Strong
hydrogen-bonding interactions occur between proton donors and proton
acceptors. Dielectric interactions favour the dissolution of ionic
molecules in polar solvents. The total interaction of the solvent and
sample is the sum of the four interactions. The total interaction for a
sample or solvent molecule in all four ways is known as the "polarity" of
the molecule. Polar solvents dissolve polar molecules and, for normal
phase partition chromatography, solvent strength increases with solvent
polarity, whereas solvent strength decreases with increasing polarity
in reverse-phase systems. The subject is discussed in detail in Snyder
and Kirkland [10].
-----------------------------Subject: 24. Extraction Techniques
24.1
Refer to Section 19.3 for some critical data on common supercritical fluids.
Supercritical fluids have been investigated since last century, with the
strongest commercial interest initially focusing on the use of supercritical
toluene in petroleum and shale oil refining during the 1970s. Supercritical
water is also being investigated as a means of destroying toxic wastes, and
as an unusual synthesis medium [1]. The biggest interest for the last decade
has been the applications of supercritical carbon dioxide, because it has
a near-ambient critical temperature (31C), thus biological materials can
be processed at temperatures around 35C. The density of the supercritical
CO2 at around 200bar pressure is close to that of hexane, and the solvation
characteristics are also similar to hexane, thus it acts as a non-polar
solvent. Around the supercritical region CO2 can dissolve triglycerides at
concentrations up to 1% mass. The major advantage is that a small reduction
in temperature, or a slightly larger reduction in pressure, will result in
almost all of the solute precipitating out as the supercritical conditions
are changed or made subcritical. Supercritical fluids can produce a
product with no solvent residues. Examples of pilot and production scale
products include decaffeinated coffee, cholesterol-free butter, low-fat meat,
evening primrose oil, squalene from shark liver oil. The solvation
characteristics of supercritical CO2 can be modified by the addition of an
entrainer, such as ethanol, however some entrainer remains as a solvent
residue in the product, negating some of the advantages of the "residue-free"
extraction.
There are other near-ambient temperature supercritical fluids, including
nitrous oxide and propane, however there are safety issues with some of them.
There are several introductory texts on supercritical fluid extraction,
including some the ACS Symposium series [2-4]. There are also a large
number of articles on applications of the technique, including processing [5],
extraction of natural products [6], and chemical synthesis [7]. The major
concentration of information occurs in the various proceedings of the
International Symposium on Supercritical Fluids [8]. There is also a Journal
of Supercritical Fluids.
24.4
What is pH?
m H )
pH and generated voltage becomes nonlinear at high pH values. The slope tends
to diminish both as the electrode ages, and at high pH. As the electrode has
a very high impedance, typically 250 Megohms to 1 Gigohm, it is necessary to
use a very high impedance measuring instrument.
The reference electrode has a fairly constant potential, but it is
temperature dependent, and also varies with activity of the silver ions in
the reference electrode. This occurs if a contaminant enters the reference
electrode.
Calibration
From the preceding, it is obvious that frequent calibration and adjustment of
pH meters are necessary. To check the pH meter, at least two standard buffer
solutions are used to cover the range of interest. The pH meter should be
on for at least 30 minutes prior to calibration to ensure that all components
are at thermal equilibrium, and calibration solutions should be immersed for
at least a minute to ensure equilibrium.
First use the buffer at pH 7, and adjust the
Then, after thorough rinsing with water, use
slope. This cycle in repeated at least once,
are necessary. Many modern pH meters have an
which requires each buffer only once.
Errors
People assume pH measurements are accurate, however many potential errors
exist. There can be errors caused by the pH-sensitive glass, reference
electrode, electrical components, as well as externally generated errors.
Glass Electrode Errors
The pH-sensitive glass can be damaged. Major cracks are obvious, but minor
damage can be difficult to detect. If the internal liquid of the pH-measuring
electrode and the external environment are connected, a pH value close to 7
will be obtained. It will not change when the electrode is immersed in a
known solution of different pH. The electrical resistance of the glass
membrane will also be low, often below 1 megohm, and it must be replaced.
Similar results occur if the glass wall between the inner and outer part of
a combined electrode breaks. This may occur if the outer part is plastic.
The inner part can crack without any external signs. The electrical
resistivity over the glass electrode is intact, but actual measuring between
both electrodes reveals a low resistivity. The electrode must be replaced.
The glass can wear out. This gives slow response times, as well as a lower
slope for the mV versus pH curve. To rejuvenate, immerse the electrode in a
3 Molar KCl solution at 55 degrees Celsius for 5 hours. If this does not
solve the problem, try removing a thin layer of the glass by immersion for
two minutes in a mixture of HCl and KF (be careful, do not breathe the fumes,
and wear gloves). The electrode is then immersed for two more minutes in HCl,
and rinsed thoroughly. As an outer layer of glass has been removed, the new
surface will be like a new electrode, however the thinner glass will result
in a shorter electrode life. Frequent recalibration will be required for
several days.
The glass can be dirty. A deposit on the glass will slow the response time,
make the response sensitive to agitation and ionic strength, and also give
the pH of the film, not the sample solution. If the deposit is known, use a
appropriate solvent to remove it, and rehydrate the electrode in 3M KCl.
If the deposit is not known, first immerse the electrode for a few minutes
in a strongly alkaline solution, rinse thoroughly, and immerse it in a
strong acid (HCl) solution for several minutes. If this does not help, try
using pepsin in HCl. If still unsuccessful, use the above HCl/KF method.
Reference Electrode Errors
The diaphragm of the reference can become blocked. This is seen as unstable
or wrong pH measurements. If the electrical resistivity of the diaphragm is
measured, high values are reported (Most multimeters will give an over-range
error). The most common reason is that AgS formed a precipitate in the
diaphragm. The diaphragm will be black in this case. The electrode should be
immersed in a solution of acidic thiourea until the diaphragm is white, and
then replace the internal filling liquid of the reference electrode
There is no contact across the diaphragm, due to air bubbles. This appears
as if the diaphragm were blocked, except that the diaphragm is white. Ensure
that the filling solution level in the reference electrode is always well
above the sample, so that liquid is always slowly flowing from the reference
electrode towards the sample.
The electrode filling solution is contaminated. This appears as unstable or
wrong pH measurements. Often the 0mV pH differs considerably from pH 7. The
diaphragm has its normal colour and the electrical resistivity is normal.
However, the solution often becomes contaminated due to low filling solution
levels, and air bubbles may also appear in the diaphragm, which obviously
affects electrical resistivity. Replacing the reference filling solution
several times should solve the problem, but the electrode may have been
permanently damaged. The problem can be avoided by choosing gel-filled
reference electrodes, double-junction electrodes, or ensuring there is an
outflow of reference filling solution towards the sample.
The electrode was filled with the wrong reference solution. This appears as
as displaced pH measurements. Flush and replace the reference liquid.
Electrical errors
Condensation or sample contamination of the electrode connecting cable. This
appears as an almost-constant measurement of about pH 7, even when the pH
electrode is disconnected from the cable, or as a pH which changes less than
it should, when tested with two standard solutions. If the cable is
disconnected from the meter, the pH will start to drift.
There is a short circuit in the cable. The symptoms are similar to the above
case, except that bending the cable may create sharp, spurious readings. In
most pH cables, between the two copper conductors there are two layers which
appear to be insulators. The inner layer is an insulator, whereas the outer
layer is a conductor to avoid trace electrical effects. If this outer layer
does contact the inner conductor, there will be a short circuit. Replace
suspect cables.
The input stage of the meter is contaminated with conducting liquid. The
symptoms are the same as above, except that removing the cable has no
effect. Closely examine the input stage of the meter for liquid or deposits.
If present, rinse with distilled water, then ethanol, and dry thoroughly.
The input stage of the meter is faulty. This gives random measurements.
Shorting both input wires does not make any difference. Repair the meter.
The input stage appears faulty. Shorting both input wires gives a stable
pH measurement of about 7. The meter may be faulty, but probably the problem
Crude oil consists mainly of hydrocarbons with carbon numbers between one and
forty. The petroleum refinery takes this product and refines it into several
fuel fractions that are optimised for their intended application. For spark
ignition engines, the very volatile and branched chain alkane hydrocarbons
have desirable combustion properties, and several fractions are produced.
CNG ( Compressed Natural Gas ) is usually around 70-90% methane with 10-20%
ethane, 2-8% propanes, and decreasing quantities of the higher HCs up to
pentane. The major disadvantage of compressed gaseous fuels is the reduced
range. Vehicles may have between one to three cylinders ( 25 MPa, 90-120
litre capacity), and they usually provide about 50% of the gasoline range.
LPG ( Liquefied Petroleum Gas ) is predominantly propane with iso-butane
and n-butane. It has one major advantage over CNG, the tanks do not have
to be high pressure, and the fuel is stored as a liquid. The fuel offers
most of the environmental benefits of CNG, including high octane - which
means higher compression, more efficient, engines can be used. Approximately
20-25% more fuel than gasoline is required, unless the engine is optimised
( CR 12:1 ) for LPG, in which case there is no decrease in power or any
significant increase in fuel consumption [4,5].
Gasoline contains over 500 hydrocarbons that may have between 3 to 12
carbons, and gasoline used to have a boiling range from 30C to 220C at
atmospheric pressure. The boiling range is narrowing as the initial boiling
point is increasing, and the final boiling point is decreasing, both
changes are for environmental reasons. A detailed description of the
composition of gasoline, along with the properties and compositions of CNG,
LPG, and oxygenates can be found in the Gasoline FAQ, which is posted monthly
to rec.autos.tech.
Kerosine is a hydrocarbon fraction that typically distils between 170-270C
(narrow cut kerosine, or Jet A1) or 100-250C ( wide cut kerosine, or JP-4 ).
It contains around 20% of aromatics, however the aromatic content will be
reduced for high quality lighting kerosines, as the aromatics reduce the
smoke point. The major use for kerosines today is as aviation turbine (jet)
fuels. Special properties are required for that application, including high
flash point for safe refuelling ( 38C for Jet A1 ), low freezing point for
high altitude flying ( -47C for Jet A1 ), and good water separation
characteristics. Details can be found in any petroleum refining text and
Kirk Othmer.
Diesel is used in compression ignition engines, and is a hydrocarbon fraction
that typically distils between 250-380C. Diesel engines use the Cetane
(n-hexadecane) rating to assess ignition delay. Normal alkanes have a high
cetane rating, ( nC16=100 ) whereas aromatics ( alpha methylnaphthalene = 0 )
and iso-alkanes ( 2,2,4,4,6,8,8-hexamethylnonane = 15 ) have low ratings,
which represent long ignition delays. Because of the size of the hydrocarbons,
the low temperature flow properties control the composition of diesel, and
additives are used to prevent filter blocking in cooler temperatures. There
are usually summer and winter grades. Environmental legislation is reducing
the amount of aromatics and sulfur permitted in diesel, and the emission of
small particulates ( diameters of <10um ) that are considered possibly
carcinogenic, and are known to cause other adverse health effects. Details
can be found in any petroleum refining text and Kirk Othmer.
27.3
Oxygenates are just pre-used hydrocarbons :-). They contain oxygen, which can
not provide energy, but their structure provides a reasonable anti-knock
value, thus they are good substitutes for aromatics, and they may also reduce
the smog-forming tendencies of the exhaust gases [6]. Most oxygenates used
in gasolines are either alcohols ( Cx-O-H ) or ethers (Cx-O-Cy), and contain
1 to 6 carbons. Alcohols have been used in gasolines since the 1930s, and
MTBE was first used in commercial gasolines in Italy in 1973, and was first
used in the US by ARCO in 1979. The relative advantages of aromatics and
oxygenates as environmentally-friendly and low toxicity octane-enhancers are
still being researched.
Ethanol
C-C-O-H
C2H5OH
C
|
C-C-O-C
|
C
C4H9OCH3
They can be produced from fossil fuels eg methanol (MeOH), methyl tertiary
butyl ether (MTBE), tertiary amyl methyl ether (TAME), or from biomass, eg
ethanol(EtOH), ethyl tertiary butyl ether (ETBE)). MTBE is produced by
reacting methanol ( from natural gas ) with isobutylene in the liquid phase
over an acidic ion-exchange resin catalyst at 100C. The isobutylene was
initially from refinery catalytic crackers or petrochemical olefin plants,
but these days larger plants produce it from butanes.
Oxygenates have significantly different physical properties to hydrocarbons,
and the levels that can be added to gasolines are controlled by the EPA in
the US, with waivers being granted for some combinations. Initially the
oxygenates were added to hydrocarbon fractions that were slightly-modified
unleaded gasoline fractions, and these were commonly known as "oxygenated"
gasolines. In 1995, the hydrocarbon fraction was significantly modified, and
these gasolines are called "reformulated gasolines" ( RFGs ). The change to
reformulated gasoline requires oxygenates to provide octane, but also that
the hydrocarbon composition of RFG must be significantly more modified than
the existing oxygenated gasolines to reduce unsaturates, volatility, benzene,
and the reactivity of emissions.
Oxygenates that are added to gasoline function in two ways. Firstly they
have high blending octane, and so can replace high octane aromatics
in the fuel. These aromatics are responsible for disproportionate amounts
of CO and HC exhaust emissions. This is called the "aromatic substitution
effect". Oxygenates also cause engines without sophisticated engine
management systems to move to the lean side of stoichiometry, thus reducing
emissions of CO ( 2% oxygen can reduce CO by 16% ) and HC ( 2% oxygen can
reduce HC by 10%)[7]. However, on vehicles with engine management systems,
the fuel volume will be increased to bring the stoichiometry back to
the preferred optimum setting. Oxygen in the fuel can not contribute
energy, consequently the fuel has less energy content. For the same
efficiency and power output, more fuel has to be burnt, and the slight
improvements in combustion efficiency that oxygenates provide on some
engines usually do not completely compensate for the oxygen.
There are huge number of chemical mechanisms involved in the pre-flame
reactions of gasoline combustion. Although both alkyl leads and oxygenates
are effective at suppressing knock, the chemical modes through which they
act are entirely different. MTBE works by retarding the progress of the low
temperature or cool-flame reactions, consuming radical species, particularly
OH radicals and producing isobutene. The isobutene in turn consumes
additional OH radicals and produces unreactive, resonantly stabilised
radicals such as allyl and methyl allyl, as well as stable species such as
allene, which resist further oxidation [8,9].
The major concern with oxygenates is no longer that they may not be
effective at reducing atmospheric pollution, but that their greater water
solubility, and very slow biodegradability, can result in groundwater
pollution that may be difficult to remove. Their toxicological and
environmental effects are also still being researched.
27.4
What is naphtha?.
White spirits are petroleum fractions that boil between 150-220C. They can
have aromatics contents between 0-100%, and Shell lists eight grades with
aromatics contents below 50%, and six grades with aromatics contents above
50%. The two common "white spirits" are defined by British Standard 245,
which states Type A should have aromatics content of less that 25% v/v and
Type B should have an aromatics content of 25-50% v/v. The most common
" white spirit" is type A, and it typically has an aromatics content of
20%, boils between 150-200C, and has an aniline point of 58C, and is
sometimes known as Low Aromatic White Spirits. The next most common is
Mineral Turpentine (aka High Aromatic White Spirits ), which typically has
an aromatics content of 50%, boils between 150-200C and has an aniline
point of 25C. For safety reasons, most White Spirits have Flash Points
above ambient, and usually above 35C. Note that "white gas" is not white
spirits, but is a volatile gasoline fraction that has a flash point below
0C, which is also known by several other names. Do not confuse the two
when purchasing fuel for camping stoves and lamps, ensure you purchase the
correct fuel.
27.7
Biofuels are produced from biomass ( land and aquatic vegetation, animal
wastes, and photosynthetic organisms ), and are thus considered renewable
within relatively short time-frames. Examples of biofuels include wood,
dried animal dung, methyl esters from triglyceride oils, and methane from
land-fills. The renewable aspect of most biofuels is essentially the use
of solar energy to grow crops that can be converted to energy. There is
a large monograph "Fuels from Biomass" in Kirk Othmer, and the subject
is frequently discussed in alt.energy.renewable, sci.energy, and
sci.energy.hydrogen.
27.8
Diesel engines can run on plant and animal triglycerides such as tallow
and seed oils, however most trials have resulted in reduced engine life, or
increased service costs. The solution is to transesterify the triglycerides
into esters, taking care to avoid the formation of monoacylglycerides
that will precipitate out at low temperatures or when diesel is encountered.
There are several plants in Austria that produce Rapeseed Oil Methyl Esters
as fuels for diesel engines. The economics of the process are very
dependant on the price of diesel and the market for the glycerol byproduct.
The common catalysts used to transesterify triglycerides are sodium
hydroxide, sodium methoxide and potassium carbonate. If the esters are to
be blended with diesel fuel, then a two stage reaction is usually required
to ensure that monoacylglycerides are kept below 0.05%. Usually this
involves using 22g of methanol ( containing 0.6g of sodium hydroxide ) and
100g of tallow refluxed for 30 minutes. The mixture is cooled, the glycerol
layer removed, and a further 0.2g of sodium hydroxide is reacted for 5
minutes at 35C in a stirred reactor. The glycerol phase is allowed to
separate, and the ester phase is washed with water to remove residual
catalyst, glycerol and methanol. Note that sodium hydroxide is the most
cost-effective catalyst, but also has the worst tendency to form soaps.
The catalyst and methanol can be of industrial grade without further
purification required, however care should be taken to prevent additional
water entering the reaction [10].
The fuel can be converted into other esters, such as ethyl and butyl, but
it really depends on the availability of cheap alcohol along with the
desired properties of the fuels. The effect of catalysts, reagent ratio,
temperature, and moisture on the production of methyl, ethyl, and butyl
esters from some common oils has been investigated [11]. The New Zealand
government investigated a wide range of techniques for turning various
vegetable and animal triglycerides into esters for diesel, and the reports
cover many aspects of the kinetics and efficiencies [12]. There is a general
overview of the current processes and technology available in Inform [13].
A specific technique for analysing the monoglycerides has been published
[14], however I have found that acetylation followed by narrow bore
( 0.1mm ID ) capillary chromatography is faster and cheaper.
enantiomer had been sold, then the tragic defects would have been avoided.
Unfortunately, thalidomide is optically unstable in solution; the pure
isomers of thalidomide racemise by the opening of the phthalimide ring, with
half-lives of 4-5 hours in buffer at pH 7.4, and less than 10 minutes in the
blood. Thus shortly after administration of either enantiomer, the other
enantiomer will be present in significant quantities [1].
Some recent work has revealed that thalidomide inhibits the production of
tumour necrosis factor alpha. Elevated levels of TNF-alpha are associated
with several inflammatory conditions. This has led to the development of
analogues that are chirally stable in reconstituted human plasma, and which
are undergoing development as anti-inflammatory drugs [2].
The recycle codes for plastics are currently being reviewed, and new codes
( probably inside a totally different symbol ) will soon be introduced.
1
2
3
4
5
6
7
=
=
=
=
=
=
=
PET
High density polyethylene
Vinyl
Low density polyethylene
Polypropylene
Polystyrene
Others, including multi-layer
The are several techniques, but the one of most interest to the public is
the system being used to identify grossly polluting vehicles. The system
consists of an infra-red source on one side of the road, and a detector
system on the other. The collimated beam of IR is directed at a gas filter
radiometer equipped with two liquid-nitrogen-cooled indium antimide
photovoltaic detectors. The beam is split, and passes through a 4.3um
bandpass filter to isolate the CO2 spectral region, a 4.6um filter to
isolates the CO region, and a third filter to isolate the HC region.
A non-absorbing region is also used to compensate for signal strength.
There are various specific enhancements, such as the spinning gas-filter
correlation cell in the University of Denver FEAT ( Fuel Efficiency
Automobile Test ) system used to cost-effectively identify grossly-polluting
vehicles [1]. "Optical remote sensing for air pollutants - review " by
M.Simonds et al [2], provides a good introduction to the diverse range of
instruments used for remote sensing of pollutants.
31.2
What is Goretex?.
31.5
The final cause is the production of nitrogen from 10s of grams of sodium
azide, but there are some extra chemicals involved along the way.
Sodium azide is toxic, The airbag inflators are aluminium-encased units
that contain an igniter (squib), gas generating pellets ( or wafers of
sodium azide propellant ), and filters to screen out combustion products.
The electrical signal ignites a few milligrams of initiator pyrotechnic
material. The pyrotechnic material then ignites several grams of booster
material, which ignites the tens of grams of sodium azide, and the azide
burns very rapidly to produce nitrogen gas and sodium.
The sodium azide is pelletised to control the rate of gas generation by
controlling its surface area. The free sodium would form sodium
hydroxide when it contacts the water in people's noses, mouths, and
eyes so, to prevent this, the manufacturers mix in chemicals that will
produce sodium salts ( silicates, aluminates, borates ) on combustion.
Inflator units also often have a layer of matted material of alumina and
silica called Fiberfrax in the particulate filter. The Fiberfrax mat reacts
with most of the remaining free sodium in the generated gas. A typical
reaction pathway is as follows [6];300C
2 NaN3 ------> 2 Na + 3 N2
10 Na + 2 KNO3 ------> K2O + 5 Na20 + N2
K2O + Na2O + SiO2 ------> alkaline silicate glass.
There are apparently also corn starch and talcum powder used as lubricants
in the bag, and if the bag explodes these are the powders that contaminate
people - not the toxic chemicals in the inflator.
One article quotes 160 grams of propellant for a drivers-side bag
( 60 litres of gas) and 450 grams for a passengers-side bags
( which are 3-5 times larger) . I suspect that may include all of the
above ingredients in the igniter, but not the bag lubricants.
The bag fills until it reaches slightly above atmospheric pressure, and
the manufacturers now control the bag inflation speed to 90-200mph, which
is less than the early models - because they were too violent and could
harm occupants. The actual sequence goes something like:0
15
18
21
45
Impact
20 milliseconds
23 milliseconds
27 milliseconds
50 milliseconds
undisturbed, you can either apply flowers of sulfur ( fine elemental sulfur )
or zinc dust, with vigorous brushing to facilitate contact, and sweep up the
excess. If the mercury is going to be re-exposed ( by cleaning, foot traffic
etc., ), then the zinc dust may be preferred because of an apparently faster
reaction rate. However, if you have a light-coloured carpet, pouring yellow
or grey powder is not usually an option, and if the location is warm and not
well-ventilated near ground level, ensure that toddlers do not spend hours
every day playing there.
There have been several studies on the best methods to clean up spills,
including "Vaporisation of Mercury spillage" [13]. The abstract reports " A
report on an investigation of the problem in laboratories and industries of
mercury (Hg) vaporisation from small droplets in cracks and floors. The
efficacy of other fixing agents besides flowers of sulfur was metered.
The results show that the use of a sulfur, calcium oxide and water mixture
was the most successful mixture for fixing mercury droplets. A second
convenient technique is the use of an aerosol hair spray. A chelating soap
is available in some countries, and this would presumably be the method of
choice in dealing with spillages."
Another article includes methods based on amalgamating with zinc impregnated
in a metal sponge or scrubbing pad for picking up mercury [14], and another
investigates substances that can be used to remove spilled mercury - such as
iodised activated carbon, copper or zinc powders, molecular sieves of copper
or silver ions, and silica gel [15].
Dental amalgam is apparently a finely divided powder of a silver, tin,
and copper alloy that is mixed with the mercury. The setting time probably
is a function of the slow dissolution of the alloy in the mercury due to
the particle size of the powder used. The mass % of each individual metal
amalgam when mercury is saturated at 20C is Ag = 0.04, Cu = 0.0032, and
Sn = 0.62, but I've no idea if that is the ratio actually used. I presume
the ratio may be varied to obtain the desired physical properties, and that
there would be a theoretical excess of the alloy to ensure minimal free
mercury. The actual amount of mercury vapour from dental amalgam is low, but
directly measurable by sensitive mercury vapour analysers. The significance
of mercury vapour from dental amalgam to health has been very controversial,
however there are now practical alternatives in widespread use.
31.7
From this we see 21 people were killed, the half life was fairly short for
the contaminants. Long term effects were probably negligible.
31.8
Most countries have food regulations that permit the use of acetic acid as
clearly-labelled "synthetic white vinegar". Most vinegars are actually malt
vinegars ( fermented ), and synthetic acetic acid is not allowed to be sold
as Malt Vinegar. Most natural, unfortified, malt vinegars are appropriately
labelled. The classification can get rather messy when bulk suppliers dilute
malt vinegar concentrates with acetic acid, which itself could either be
synthetic, or from another fermentation process. Regulations usually require
any addition of acetic acid to be clearly marked on the label, and the
product is not normally legally sold as pure "malt vinegar". The amount of
acetic acid in "natural" malt, cider, or wine vinegars usually ranges from
4% - 6%, but some examples can have up to approximately 20%. Vinegar is
produced by the exothermic aerobic bacterial oxidation of ethanol to acetic
acid via acetaldehyde.
31.10 What are the different grades of laboratory water?.
There are several techniques used in chemical laboratories to obtain the
required purity of water. There are several grading systems for water, but
the most well-known is the ASTM system, although certain applications (HPLC)
often require purer water than ASTM Type I, consequently additional
treatments such as ultrafiltration and UV oxidation may also be used to
reduce concentrations of uncontrolled impurities, such as organics.
ASTM Type
Specific Conductance
Specific Resistance
Total Matter
Silicate
KMnO4 Reduction
(max. uMhos/cm.)
(min. Mohms/cm.)
( max. mg/l )
( max. mg/l )
( min. mins )
Type
Colony Count (Colony forming units/ml)
pH
I
<0.06
>16.67
<0.1
N/D
>60.0
A
0 Bacteria
NA
II
<1.0
>1.0
<0.1
N/D
>60.0
B
<10
NA
III
<1.0
>1.0
<1.0
0.01
>10.0
C
<100
6.2-7.5
Newsgroups: sci.chem
Subject: Sci.chem FAQ - Part 7 of 7
Date: Thu, 15 Jan 2004 22:13:09 +1300
Message-ID: <0cmc005it9tiu2vnt3umkmkvvkb4bqift4@4ax.com>
Reply-To: B.Hamilton@irl.cri.nz
Archive-name: sci/chem-faq/part7
Posting-Frequency: monthly
Last-modified: 22 October 1999
Version: 1.17
31.11 What is Sarin nerve gas?.
Sarin is a nerve gas that was used in 1988 by Iraq against its Kurdish
population, and in 1995 by Japanese terrorists against Tokyo subway users.
Sarin and its companion nerve gases ( Tabun and Soman ) were discovered
in the late 1930s by Gerhard Schrader at I.G.Farben during research into
pesticides. The lethal dose for humans may be as low as 0.01mg/kg [18],
unless treated immediately. Sarin inhibits acetylcholinesterase, an enzyme
that breaks down acetylcholine. Acetylcholine carries signals between nerves
and muscles, and build-up causes over-stimulation of muscles ( including
the involuntary ones controlling eye, lungs, bowel ), which then go into
spasms. Treatment involves atropine ( shuts down the overstimulated nerves ),
or oxime drugs ( can prise Sarin off the enzyme ), and must be immediate.
More details and references can be found in the Merck Index.
There are many different methods of manufacture, but the Tokyo product
appears to have been prepared using a procedure involving phosphorus
trichloride and methyl iodide. The product was impure and diluted with
acetonitrile to improve volatility. To stockpile Sarin, the product has to
be pure ( 90-99% of the Iraqi Sarin degraded in < 2 years, whereas US Sarin
only degraded a few % over 30 years ). The standard US government procedure
( aka "di-di" ) starts with dimethyl methylphosphonate (DMMP), and ends
with a distillation to remove impurities [19].
O
O
O
O
CH3
||
thionyl
||
HF
|| isopropyl
||
/
CH3-P-OCH3 ------> CH3-P-Cl --> CH3-P-F ---------> CH3-P-O-CH
|
chloride
|
|
alcohol
|
\
OCH3
Cl
F
F
CH3
DMPP
Dichlor
Difluor
Sarin (GB)
1
9
2/ \ ___ / \8
| O |_o_| O |
3\ /
\ /7
4
6
Dibenzo-p-dioxin
Dibenzofuran
As dioxins are fat soluble, they will accumulate in fatty tissue. In general,
it is only the biologically active ( molecules containing the 2,3,7,8
substitution ) congeners that accumulate, with levels of the higher
to fuse tritium atoms. Experts are sceptical that such an energetic compound
could be sufficiently stable to be used as an explosive, and no compelling
evidence for the existence of red mercury has yet been produced.
31.14 How do I remove stains and deposits?
- Test any planned treatment on an unimportant part of the material first,
(spots and holes aren't currently fashionable ).
- Chemicals for removing stains are often toxic and corrosive, handle with
care, and follow any provided safety instructions.
- Often stains are a diverse mix of chemicals, and the best solution is
to solubilise as much as possible, remove insoluble material through
washing, and then carefully bleach. Chemists should not assume they can
perform this process better than housewives.
- Some stains are more easily removed by physical means - such as using
abrasives ( household cleaning pastes, steel wool, metal polishes, etc ),
or freezing solid and scraping ( chewing gum ).
- The fresher the stain, the easier to remove. Avoid using hot water or soap
on unknown stains, and use solvents (eg glycerine) to help keep the stain
fresh. In cases when the stain is known to be water-soluble (eg bird
droppings ), it is often preferable to allow the stain to dry and carefully
scrape most away, before additional treatment.
- When using solvents, apply around the outer edge of the stain and work
towards the centre to prevent a stain ring forming.
- Many stains result from pigments, and they are seldom soluble, so once the
other components are removed, use physical agitation to remove the
insoluble material.
- Sometimes a dried stain can be "freshened" by using more of the stain
before treating - but use this approach very cautiously.
There are books on stain removal [25,26,27], and many of the common recipes
are also often found in some home-care and cookery books. Home-care magazines
also have question and answer sections that frequently include advice on
how to remove specific stains. Very few chemical books cover chemical
cleaning and stain removal, and smart chemists avoid offering to remove
stains :-). Common stains are usually attacked with the household chemical
arsenal that may include:* Absorbents - Cornflour, French chalk, fuller's earth, starch, talcum powder.
* Acids - Inorganic = hydrochloric ( galvanising remover, concrete cleaner ).
- Organic = acetic ( white vinegar ), citric ( lemon juice ),
tartaric ( cream of tartar )
* Alkalis - Sodium hydroxide ( drain cleaner ), ammonia solution,
* Bleaches - Sodium hypochlorite solution ( household bleach ), calcium
hypochlorite ( bleaching powder ), hydrogen peroxide
* Drycleaning Fluids - 1,1,1-trichloroethane, perchloroethylene.
* Enzymes - Pepsin
* Petroleum Fractions - mineral turpentine, kerosine, gasoline, white spirits.
* Sodium carbonate ( washing soda ), sodium bicarbonate ( baking soda ),
sodium tetraborate ( borax ).
* Solvents - Acetone ( nail polish remover ), amyl acetate, methanol, ethanol
( methylated spirits ), glycerine, toluene, xylenes, iso propyl
alcohol.
* Terpenes - Eucalyptus oil, citrus oil, camphor
Specific Stain Strategies.
Ballpoint - methylated spirits, fullers earth, glycerine.
Blood - cold salty water, cornflour paste, or dilute bleach.
Copper deposits on sink or bathtub - ammonia (1 hr) then detergent.
Chewing Gum - freeze, or sponge with eucalyptus oil.
Chocolate - methylated spirits, or soak in 5% borax solution
rubbing. The sulfide has actually dislocated some silver atoms from the metal
surface, and the cleaning treatment will not relocate them, but it will
eliminate the unsightly, dark, tarnish.
A typical procedure is to line a pyrex glass dish with alumimium foil so the
bright side of the foil will contact the solution. Add one litre of water,
and heat until near boiling. Add one tablespoon of sodium chloride and one
tablespoon of sodium bicarbonate, and gently stir to dissolve. Ensure that
the silverware has been washed in warm dishwashing detergents, and well
rinsed in warm water, to remove dirt and grease. Carefully add the silverware
to the dish, ensuring that each item is in contact with the aluminium foil,
and leave until the tarnish has disapppeared. Because no protective film
has been provided, the tarnish may reappear rapidly.
31.17 How do I electroplate or anodise materials?.
There are several excellent books and journals on metal treatments in the
hobbies and metalworking sections of public libraries. For the serious
plater, the journals Surface Finishing and Product Finishing discuss all the
the chemical and electrical aspects - including disposal and destruction of
wastes. Their Annual Handbooks, along with the Canning Handbook of
Electroplating, have many recipes and details for the serious electroplater.
In any metal finishing process, the preparation of the substrate is of
great importance, and the recommended sequence of cleaning, pickling,
plating, and especially passivating should be carefully followed.
Failure to correctly passivate newly-deposited protective surfaces is the
main cause of the rapid formation of unsightly corrosion products.
31.18 How fast do solvents pass through human skin?
It obviously depends on the solvents, and traditional measurements have
been made using dead skin, but some recent work has provided a simple
comparison of individual solvents. It must be emphasised that mixtures of
solvents may have significantly different rates [29].
Solvent
Dimethylsulfoxide
N-Methyl-2-pyrrolidone
Dimethylacetimide
Dimethylformamide
Methyl ethyl ketone
Methylene chloride
Water [^3H radiolabeled]
Ethanol
Butyl acetate
gamma butyrolactone
Toluene
Propylene carbonate
Sulfolane
pH
(when opened)
pH
(corrected)
Initial
30 seconds
60 seconds
2 minutes
4 minutes
2.75
2.78
2.80
2.82
2.80
@
@
@
@
@
7C
7C
7C
7C
7C
2.6
2.6
2.6
2.7
2.6
A sample was degassed in an ultrasonic bath for several minutes and the
pH measured, and compared to a control sample maintained at the same
temperature and time profile.
pH
Degassed pH
2.52 @ 21c
RT sample
2.50 @ 20C
So the conclusion is that the pH of Coca-Cola is approximately 2.5 - 2.7.
Not surprisingly, the relatively weak carbonic acid from the dissolved CO2
did not significantly affect the pH of the beverage. The aluminium beverage
containers are lined with a thin polymer or lacquer coating to prevent the
aluminium metal dissolving into the beverage.
Note that the differing flotation characteristics of cans of the normal
versions of carbonated beverages like Coca-Cola ( they may sink ), and
the diet versions ( they may float ), has nothing to do with the amount
of CO2 present. It is due to the increase in solution density from the
few percent of sugar added to the normal version, while the diet version
has only a few hundred ppm of an artificial sweetener that is much sweeter
than sugar.
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
Refer 6.3
[2]
Dialog
Knight-Ridder Information, Inc.
www http://www.dialog.com
email info@dialog.com
phone 800-334-2564, or 415-254-7000
fax 415-254-7070
[3]
[4]
[5]
Section 9:
[1]
[2]
[3]
[4]
[5]
[6]
J.T.Baker Inc.
222 Red School Lane
Phillipsburg. NJ 08865
Phone 800-582-2537
Fax. 908-859-9318
[7]
Refer 6.19
[8]
Refer 6.16
[9]
Refer 6.12
[2]
[3]
[4]
A.K.Furr (editor)
CRC Press (1995) ISBN 08493-2518-8
[5]
[6]
Refer 6.2
[7]
[8]
[9]
- 1990-1991
should be obtained and used.
(1990) ISBN 0-936712-87-2
Cincinnati, OH 45211-4438 )
Refer 9.36
[2]
Refer 9.37
[3]
Refer 9.40
[4]
Refer 9.39
[5]
Refer 9.41
[6]
[7]
Refer 9.24
[8]
[9]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
The Sassafras Tree and Designer Drugs - From Herbal Tea to Ecstasy.
L.G.French
J.Chem.Ed. v.72 n.6 p.484-491. (June 1995).
[4]
[5]
[6]
Nitrogen Triiodide
I.C.Tornieporth-Oetting, T.M.Klapotke
Angew.Chem.Int.Ed.Engl. v.29 p.677-679 (1990)
[7]
[8]
[9]
ISBN 3527285067
[2]
[4]
[5]
[6]
[7]
[8]
[9]
Glowing Veggies
P.Scharlin, A.A.Cleveland, R.Battino, and M.E.Thomas.
J.Chem.Ed. v.73 n.5 p.457-459 (May 1996)
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[2]
Section 18:
[1]
Refer 15.1
[2]
[3]
Overview of Sweeteners
J.W.Ellis
J.Chem.Ed. v.72 n.8 p.671-675 (August 1995)
[4]
[5]
[6]
[7]
[8]
Refer 6.11
Chromogenic Materials v.6 p.312-343.
[9]
Electrochromic Materials
R.J.Mortimer
Chem.Soc.Revs. v.26 p.147-156 (1997)
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
Refer 11.15
[2]
[3]
Polarized Light.
W.A. Shurcliff and S.S. Ballard
Princeton: D. Van Nostrand, (1964)
[4]
[5]
[6]
[7]
[8]
Section 22:
[1]
Refer 11.13
[2]
Refer 11.14
[3]
Refer 11.15
[4]
Refer 11.16
Section 23:
[1]
[2]
[4]
Refer 11.30
[5]
Refer 11.31
[6]
[7]
[8]
[9]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
Section 26:
[1]
[2]
[3]
[4]
Section 27:
[1]
[2]
[3]
Refer 27.1
- Chapter 9. R.E.Banks and P.J.King.
[4]
Refer 27.1
- Chapter 20. K.Owen.
[5]
[6]
[7]
[8]
[9]
[2]
Section 31:
[1]
[2]
[3]
[4]
[5]
Goretex patent
U.S. Pat. 3,962,153 (8 June 1976) R.W.Gore (to W.L.Gore and Associates)
[6]
[7]
[8]
[9]
Dichlor
Difluor
Sarin (GB)
1
9
2/ \ ___ / \8
| O |_o_| O |
3\ /
\ /7
4
6
Dibenzo-p-dioxin
Dibenzofuran
As dioxins are fat soluble, they will accumulate in fatty tissue. In general,
it is only the biologically active ( molecules containing the 2,3,7,8
substitution ) congeners that accumulate, with levels of the higher
homologues predominating [20]. It is important to remember that of all the
dioxins and furans, only those containing 4 to 8 chlorine atoms, _and_ with
chlorine atoms in the 2,3,7,8 positions are currently considered toxic.
A typical procedure is to line a pyrex glass dish with alumimium foil so the
bright side of the foil will contact the solution. Add one litre of water,
and heat until near boiling. Add one tablespoon of sodium chloride and one
tablespoon of sodium bicarbonate, and gently stir to dissolve. Ensure that
the silverware has been washed in warm dishwashing detergents, and well
rinsed in warm water, to remove dirt and grease. Carefully add the silverware
to the dish, ensuring that each item is in contact with the aluminium foil,
and leave until the tarnish has disapppeared. Because no protective film
has been provided, the tarnish may reappear rapidly.
31.17 How do I electroplate or anodise materials?.
There are several excellent books and journals on metal treatments in the
hobbies and metalworking sections of public libraries. For the serious
plater, the journals Surface Finishing and Product Finishing discuss all the
the chemical and electrical aspects - including disposal and destruction of
wastes. Their Annual Handbooks, along with the Canning Handbook of
Electroplating, have many recipes and details for the serious electroplater.
In any metal finishing process, the preparation of the substrate is of
great importance, and the recommended sequence of cleaning, pickling,
plating, and especially passivating should be carefully followed.
Failure to correctly passivate newly-deposited protective surfaces is the
main cause of the rapid formation of unsightly corrosion products.
31.18 How fast do solvents pass through human skin?
It obviously depends on the solvents, and traditional measurements have
been made using dead skin, but some recent work has provided a simple
comparison of individual solvents. It must be emphasised that mixtures of
solvents may have significantly different rates [29].
Solvent
Dimethylsulfoxide
N-Methyl-2-pyrrolidone
Dimethylacetimide
Dimethylformamide
Methyl ethyl ketone
Methylene chloride
Water [^3H radiolabeled]
Ethanol
Butyl acetate
gamma butyrolactone
Toluene
Propylene carbonate
Sulfolane
pH
(when opened)
2.75 @ 7C
2.78 @ 7C
2.80 @ 7C
pH
(corrected)
2.6
2.6
2.6
2 minutes
4 minutes
2.82 @ 7C
2.80 @ 7C
2.7
2.6
A sample was degassed in an ultrasonic bath for several minutes and the
pH measured, and compared to a control sample maintained at the same
temperature and time profile.
pH
Degassed pH
2.52 @ 21c
RT sample
2.50 @ 20C
So the conclusion is that the pH of Coca-Cola is approximately 2.5 - 2.7.
Not surprisingly, the relatively weak carbonic acid from the dissolved CO2
did not significantly affect the pH of the beverage. The aluminium beverage
containers are lined with a thin polymer or lacquer coating to prevent the
aluminium metal dissolving into the beverage.
Note that the differing flotation characteristics of cans of the normal
versions of carbonated beverages like Coca-Cola ( they may sink ), and
the diet versions ( they may float ), has nothing to do with the amount
of CO2 present. It is due to the increase in solution density from the
few percent of sugar added to the normal version, while the diet version
has only a few hundred ppm of an artificial sweetener that is much sweeter
than sugar.
32. References
Note: "Refer 6.1" = Section 6, Reference 1.
Section 6:
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
Book & CD-Rom edition John Wiley & Sons (November 1999) ISBN 0471378585
[21] Shreve's Chemical Process Industries - 5th edition
R.N.Shreve and G.T.Austin
McGraw Hill (1984) ISBN 0-07-057147-3
[22] Ullmann's Encyclopedia of Industrial Chemistry - 6th edition.
Editors, J.E.Bailey, J.Brinder, M.Bohnet
VCH. Book & CD-Rom edition (July 1999) ISBN 3527201637
[23] Vogel's Textbook of Quantitative Chemical Analysis - 5th edition
A.I.Vogel
(previously Vogel's Textbook of Quantitative Inorganic Analysis )
5th Ed. (revised by G.H.Jeffery et al) Longman (1989) ISBN 0-470-21517-8
4th Ed. (revised by J.Bassett et al.) Longman (1978) ISBN 0-582-46321-1
3rd Ed. Longman (1962) ISBN 0-582-44247-8
(Note - I personally prefer the 3rd edition which was the last written
by A.I.Vogel, he provided more alternatives for each analysis,
especially for titrations )
[24] Vogel's Qualitative Inorganic Analysis - 7th edition
A.I.Vogel
( previously Macro and Semi-micro Qualitative Inorganic Analysis )
7th Ed. ( revised by G.Svehla ) Longmans (1996) ISBN 058-221866-7
4th Ed. Longmans (1954) SBN 582 44246 X
( Note - I've never seen the 7th edition - I'm very happy with the 4th
edition, which was the last by A.I.Vogel )
[25] Vogel's Textbook of Practical Organic Chemistry - 5th edition
A.I.Vogel
5th Ed. (revised by A.R.Tatchell et al) Wiley (1989) ISBN 0582-46236-3
4th Ed. (revised by B.S.Furniss et al) Longman (1978) ISBN 0582-44250-8
3rd Ed. Longmans (1956)
( Note - the 3rd edition was the last by A.I.Vogel, but the 4th has the
advantage of discussing of modern techniques. I have not seen the 5th.)
[26] Vogel's Elementary Practical Organic Chemistry - 3rd edition
A.I.Vogel. ( revised by B.V.Smith and N.M.Waldron )
Longman (1980) ISBN 0-582-47009-99v10
Section 7:
[1]
Refer 6.3
[2]
Dialog
Knight-Ridder Information, Inc.
www http://www.dialog.com
email info@dialog.com
phone 800-334-2564, or 415-254-7000
fax 415-254-7070
[3]
[4]
[5]
Section 9:
[1]
[2]
[3]
[4]
[5]
[6]
J.T.Baker Inc.
222 Red School Lane
Phillipsburg. NJ 08865
Phone 800-582-2537
Fax. 908-859-9318
[7]
Refer 6.19
[8]
Refer 6.16
[9]
Refer 6.12
[2]
[3]
[4]
[5]
S.G.Luxon (editor)
Royal Society of Chemistry (1992) ISBN 0-85186-229-2
[6]
Refer 6.2
[7]
[8]
[9]
- 1990-1991
should be obtained and used.
(1990) ISBN 0-936712-87-2
Cincinnati, OH 45211-4438 )
Refer 9.36
[2]
Refer 9.37
[3]
Refer 9.40
[4]
Refer 9.39
[5]
Refer 9.41
[6]
[7]
Refer 9.24
[8]
[9]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
Section 13:
[1]
The Sassafras Tree and Designer Drugs - From Herbal Tea to Ecstasy.
L.G.French
J.Chem.Ed. v.72 n.6 p.484-491. (June 1995).
[4]
[5]
[6]
Nitrogen Triiodide
I.C.Tornieporth-Oetting, T.M.Klapotke
Angew.Chem.Int.Ed.Engl. v.29 p.677-679 (1990)
[7]
[8]
[9]
ISBN 3527285067
[2]
[4]
[5]
[6]
[7]
[8]
[9]
Glowing Veggies
P.Scharlin, A.A.Cleveland, R.Battino, and M.E.Thomas.
J.Chem.Ed. v.73 n.5 p.457-459 (May 1996)
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
Section 17:
[1]
[2]
Section 18:
[1]
Refer 15.1
[2]
[3]
Overview of Sweeteners
J.W.Ellis
J.Chem.Ed. v.72 n.8 p.671-675 (August 1995)
[4]
[5]
[6]
[7]
[8]
Refer 6.11
Chromogenic Materials v.6 p.312-343.
[9]
Electrochromic Materials
R.J.Mortimer
Chem.Soc.Revs. v.26 p.147-156 (1997)
Section 19:
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
Refer 11.15
[2]
[3]
Polarized Light.
W.A. Shurcliff and S.S. Ballard
Princeton: D. Van Nostrand, (1964)
[4]
[5]
[6]
[7]
[8]
Section 22:
[1]
Refer 11.13
[2]
Refer 11.14
[3]
Refer 11.15
[4]
Refer 11.16
Section 23:
[1]
[2]
[3]
J.G.Kirchner
Wiley-Interscience (1978) ISBN 0-471-93264-7
Sigma Chemical (1990) ISBN 0-941633-25-X (reprint)
[4]
Refer 11.30
[5]
Refer 11.31
[6]
[7]
[8]
[9]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
Section 26:
[1]
[2]
[3]
[4]
Section 27:
[1]
[2]
[3]
Refer 27.1
- Chapter 9. R.E.Banks and P.J.King.
[4]
Refer 27.1
[6]
[7]
[8]
[9]
[2]
Section 31:
[1]
[3]
[4]
[5]
Goretex patent
U.S. Pat. 3,962,153 (8 June 1976) R.W.Gore (to W.L.Gore and Associates)
[6]
[7]
[8]
[9]
Phone
Fax
617-275-9200
617-275-8200
800-225-1380