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are the least reactive class of organic compounds. They contain only C-C and C-H single bonds, which have high bond enthalpies.
energetic or high temperature conditions. Alkane reactions often form mixtures of products that are difficult to separate.
The chemistry of alkanes is restricted to combustion and
substitution reactions. Radicals are the only species reactive enough to overcome the high activation energy required to break the strong C-C and C-H bonds.
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alkanes with chlorine or bromine proceeds at a moderate rate and is easily controlled. The reaction with fluorine is often too fast to control, while iodine reacts very slowly or not at all.
For example methane reacts with chlorine (Cl2) to form chloromethane,
is used to convert higher-boiling fractions (larger hydrocarbons) into smaller ones. There are two types of cracking:
a)
Catalytic hydrocracking
b)
Catalytic cracking
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particular bond homolytically, i.e., in such a way that each bonded atom retains one of the bonds two electrons.
In contrast, when a bond is broken and one of the atoms retains both
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) is used to show the movement of the electron pair in an ionic cleavage, and to show the separation of individual electrons in a homolytic cleavage.
The curved arrow begins with a covalent bond or unshared electron pair (a
site of higher electron density) and points toward a site of electron deficiency.
Remember, the curved arrow shows the movement of electrons, while the
fish hook shows the movement of one electron per atom i.e. separation.
Now, students, with all this said, what do we really mean when we speak of
mechanism.
The mechanism is the complete, step-by-step description of exactly which
bonds break and which bonds form in what order to give the observed products.
reaction.
A chain reaction consists of three kinds of steps: 1. 2.
3.
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bond. The reactions of alkenes arise from the reactivity of the carbon-carbon double bond.
The most common chemical reaction of a carbon-carbon double
bond is the addition reaction. Because single bonds (sigma bonds) are more stable than pi bonds, we might expect the double bond to react and transform the pi bond into a sigma bond.
Let us now look at the reactions of alkenes:
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Bromination
Alkenes react with bromine in the presence of an organic solvent (CCl4) to form 1,2-dibromoalkane. Note that when bromine in the presence of an organic solvent it is liquid bromine i.e. Br2 (l)
Note the organic solvent is inert, thus it does not participate in the reaction.
b)
In the presence of water, halogens add to alkenes to form halohydrins i.e. a halo alcohol. In this case, molecules of the solvent become reactants, too:
Note that when bromine reacts with an alkene in the presence of water it is aqueous bromine i.e. Br2 (aq).
Explains the steps involved in the mechanism of selected chemical reactions of alkene functional group Electrophilic Addition of Bromine
Electrophiles are species that are electron-pair acceptors. They are typically positive ions like H+ or NO2+. Electrophiles accept electron pairs to form new bonds. The bromine is a very polarisable molecule and the approaching pi bond in a molecule i.e. there will be a partial positive and a partial negative charge on each of the bromine atom, causing it to look like this: The mechanism for the electrophilic addition of bromine to alkene occurs in two steps:
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Alkenes react with warm acidified potassium manganate (VII) solution to form mixtures of ketones and carboxylic acids. To be even more specific, students, warm concentrated KMnO4 oxidizes alkenes to glycols, then cleaves the glycols. The products are initially ketones and aldehydes, but aldehydes are oxidized to carboxylic acids under these conditions.
b)
Alkenes react with cold KMnO4. If the KMnO4 solution is acidified with dilute H2SO4, the purple solution becomes colourless. The manganate (VII) ions are reduced to manganese (II) ions while the alkenes are converted to 1,2-diols.
When conc. H2SO4 adds across a carbon-carbon double bond an alkyl hydrogen sulphate is produced. When ethene is bubbled into conc. H2SO4 at room temperature, ethyl hydrogen sulphate is formed:
The structure of the product molecule is sometimes written as CH3CH2H2SO4, but the version in the equation is better because it shows how all the atoms are linked:
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Hydrogen halides
The hydrogen halides, HCl, HBr, and HI, all add across the double bond. When hydrogen bromide adds to ethene, bromoethane is formed:
When hydrogen halides add to an unsymmetrical alkene two products are possible. The addition of hydrogen bromide to prepare could give either
In fact, the product is almost entirely 2-bromopropane. The Russian chemist, Markovnikov, formulated a rule for predicting which addition product would be formed. Markovnikovs Rule can be stated: in addition of a compound HX to an unsaturated carbon atom which carries the larger number of hydrogen atoms.
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Hydrogenation
This is the process by which hydrogen is added across a double bond at high temperature in the presence of finely nickel, platinum or palladium catalyst. The process of hydrogenation is intended to add hydrogen atoms to cis-unsaturated fats, eliminating a double bond and making them more saturated. These saturated fats have a higher melting point, which makes them attractive for baking and extends their shelf-life. However, the process frequently has a side effect that turns some cis-isomers into transunsaturated fats instead of hydrogenating them completely. A natural, unsaturated fatty acid might look like the molecule below. It has several double-bonds between adjacent carbon atoms, which is what makes it unsaturated (saturated fats have no double bonds and all the species available are taken up by hydrogen atoms.
When this oil is hydrogenated, it is not possible to control where the hydrogen atoms are added to the structure. If both hydrogen atoms are added to the same side of the structure. If both hydrogen atoms are added to the same side of the structure, it is called a cis fat.
If, however, one hydrogen atom adds to one side of the structure and the other atom to the other side, it creates trans fats.
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The shape of the molecule is therefore vital to its function, much in the same way as the shape of a key is important for operation of a lock. Trans fats are straight and can pack into a crystal formation, which allows them to solidify at room temperature. Trans fats have harmful effects on blood lipids, promote inflammation, and cause blood vessel abnormalities, all of which are risk factors for heart disease. Trans fat raises your bad low-density lipoproteins (LDL) cholesterol and lowers your good (HDL) cholesterol.
Graded Worksheet
Answer all the questions below:
1. 2.
Draw and label the isomers of 3-hexene using both the cis-trans.
[4 marks]
Write and name the structural formula for the products that form when ethene reacts with each of the following reagents. [4 marks]
a) b)
3. 4.
Why do alkenes show geometrical isomerism, whereas alkanes do not? [2 marks] Outline mechanism for the electrophilic addition of HBr to 2-methyl-1-butene, and name the product. [6 marks] Name the following compounds:
a) b) c) d) e) f)
5.
[6 marks]
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carbon atom.
There are three main classes of alcohols:
Primary (10); Secondary (20) Tertiary (30)
the carbinol carbon atom i.e. the carbon bearing the OH group:
in a primary alcohol, it has one R group and two hydrogen atoms; in a secondary alcohol, it has two R groups and one hydrogen atom; in a tertiary alcohol, it has three R groups.
The most typical reactions of alcohols involve nucleophilic substitution reactions in which the OH group is replaced by an incoming group such as a halogen. Nucleophiles are species that are electron-pair donors. Nucleophiles include negatively charged ions such as CN-, OH- or Cl-, as well as molecules bearing lone pairs of electrons like H2O or NH3. Nucleophiles attack the partially positively charged (+) atoms of polar covalent bonds.
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In this reaction, it is the C(O)OH bond in the acid that breaks and not the COH bond in the alcohol.
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According to the syllabus only equations are required for the reaction of alcohol with carboxylic acid and conc. H2SO4.
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Primary (10) if there is one alkyl group attached to the carbon i.e. the
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ions hydrolyze halogenoalkanes to alcohols. Whenever a halogenoalkane is hydrolyze the corresponding alcohol is formed.
E.g. Bromoethane will form ethanol wherein the Br- is replaced by an OH
ion.
nucleophile.
Therefore
we have one nucleophile replacing another nucleophile in the hydrolysis of halogenoalkanes which in essence is a nucleophilic substitution reaction.
primary or secondary alkyhalide (halogenoalkane), the bond breaking and making processes may occur in a
concerted manner or Step-wise manner.
which both bond breaking and making are occurring at the same time.
Step-wise manner is, however, as it is suggested by its name, one
process occurring before the other. i.e. bond breaking before bond forming.
For alkylhalide to have a concerted reaction it would have to be a
primary alkylhalide.
The reason is simple students, a primary alkylhalide is unable to form
a stable carbocation intermediate to await the entry of the (-OH) hydroxide ion.
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reaction, taking place in a single step with bonds breaking and making at the same time.
Hydroxide ion attacks the backside of the electrophilic carbon atom, donating
a pair of electrons to form a new bond. (In general, nucleophiles are said to attack electrophiles, not the other way around.)
Notice that curved arrows are used to show the movement of electron pairs,
shell, so the carbon-iodine bond must begin to break as the carbon-oxygen bond begins to form.
The middle structure is a transition state, a point of maximum
partially formed and the bond to the leaving group (iodide) is partially broken.
Note students, transition state is not a discrete molecule that can
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occurs in a step-wise manner forming an intermediate in the process. Step 1: Formation of carbocation (rate-determining)
Note the long arrow is suggesting that reaction is more stable on the reactant side. The first step
is a slow ionization to form a carbocation. The second step is a fast attack on the carbocation by a nucleophile.
contain the carbonyl group. Aldehydes have the structure (as given above) where R is an alkyl or aryl group.
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Tollens reagent: the silver mirror test Tollens reagents is sometimes called ammonical silver nitrate. It is a solution of complex silver ions, [Ag(NH3)2]2+, is reduced to a silver mirror when warmed with aldehydes but not ketones. Fehlings solution Fehlings solution contains complex copper (II) ions. On warming, aldehydes reduce Fehlings solution, which is blue, to a brickred precipitate of copper (I) oxide Cu2O. (Methanal reduces to solution further to metallic copper.)
2)
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LiAlH4 in ether.
Cyanohydrin (Hydroxynitirile) Formation (NaCN/HCl) A cyanohydrin reaction is an organic chemical reaction by an aldehyde or ketone with a cyanide anion to form cyanohydrin. The CN- is a nucleophile which attacks the carbonyl group causing it to become polarize and picking the H+ of HCl.
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The evolution of CO2 from sodium hydrogen carbonate is used as a test to distinguish carboxylic acids from weaker acids, such as phenols.
The alkyl group after the ester linkage is written first. Conversion to Acid Chlorides Carboxylic acids react with SOCl2 (thionyl chloride), PCl3 (phosphorus trichloride) and PCl5 (phosphorus pentachloride) to produce acyl chlorides. The conversion of carboxylic acids to acyl chlorides using thionyl chlorides (SOCl2) is more convenient than PCl3 and PCl5 since the by-products formed, using thionyl chloride are gases.
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