!

CHEM 31.1 MIDTERMS REVIEWER!

soluble in 5% NaOH = acidic > involves acid-base

EXPERIMENT 1: SOLUBILITY OF ORGANIC

COMPOUNDS!
Solubility of a compound depends on its structure!
solubility class of an unknown compound can help in
determination of its main functional group !
solubility in certain solvents often leads to more specific
information about the functional group!
if a compound is soluble in solvent to the extent of
approximately 3-5% weight/volume or volume/volume !
do not depend solely on intermolecular forces between
the solute and solvent!
can arise from the reaction between solute and solvent!
Soluble in water & diethyl ether!
- ration of the polar groups to the number of carbon
atom is 1:4 > soluble in water!
- number of carbon atom per group is greater than 5
> insoluble or sparingly soluble in water !

NaHCO3 (weaker base than NaOH): used to determine

Water Soluble (S1 & S2)!

Functional groups that can form H-bond with water !
- Amines, Carboxylic acids, aldehyde, ketones!
Organic salts are soluble in water!
Carbon chain length: # of C must be less than 5 for
every electronegative atom!
Carbon Chain Length & Solubility!
- ex: alcohols!
- Polyhydroxy alcohols are more soluble than
monohydroxy alcohols!
- For monohydroxy alcohols, increasing chain length =
decreasing water solubility!
- Branching of alkyl group = decrease in intermolecular
forces of attraction = increase solubility in water (only
for low MW monohydroxy alcohols) !
smaller surface area exposed!
only for low mw monohydroxy alcohols!
S1 (WEAKLY POLAR)!
- soluble in water and in diethyl ether!
- Non ionic!
- contains 4 or less carbon atoms!
- contains only one strong polar group!
- In water: H-bond!
- In ether: LDF!
- Members: !
low MW aldehydes!
ketones!
monohydroxy alcohols!
aliphatic acids !
S2 (STRONGLY POLAR)!
- soluble in water, insoluble in diethyl ether!
- Ionic!
- contains 2 or more polar groups with no more than 4
carbon atoms per each polar group!
- Members:!
ionic salts of carboxylic acids!
amines !
polyhydroxylated compounds!
carbohydrates !

Acidic Compounds (A1 & A2)!

neutralisation reaction !
whether the compound is a strong or weak acid !

A1 (STRONG ACID)!
- soluble in 5% NaOH and 5% NaHCO3!
- Members:!
carboxylic acids!
phenols with electron withdrawing groups (ex:
NO2) !

- Note: carbon chain length of carboxylic acids!

- low pKa = stronger acid !
A2 (WEAK ACID)!
- soluble in 5% NaOH and insoluble in 5% NaHCO3 !
- Members:!
phenols!
amino acids!
- Note: Reaction between weak acid and weak base is
not favourable !

- do not react significantly with weak base !

Basic Compounds (B)!

Compounds which are soluble in 5% HCL!
dissolution process mainly due to the acid-base
neutralisation reaction that produces soluble organic
salts !
Members:!
- primary, secondary & tertiary amines !

Miscellaneous Compounds (M)!

insoluble in 5% HCl and contain nitrogen or sulfur atom !
Members:!
- Nitrogen-containing but not basic (ex: Amides)!
- Sulfur-containing but not acidic (ex: thioethers)!

Inert Compounds (I) !

insoluble in 5% HCl!
insoluble in concentrated sulfuric acid !
Members:!
- aliphatic (saturated) hydrocarbons!
- aromatic hydrocarbons!
- alkyl halides !
- aryl halides !
Neutral Compounds (N)!
insoluble in 5% HCl!
soluble in concentrated sulfuric acid !
- almost all compounds containing oxygen, nitrogen or
sulfur atom are easily protonated by concentrated
sulphuric acid !
reacts via forced protonation!
Members:!
- high MW alcohols!
- aldehydes!
- ketones!
- nitriles!
- esters & ethers (more than 4 carbon atom)!
- unsaturated hydrocarbons !

EXPERIMENT 2: RECRYSTALLIZATION AND MELTING

POINT DETERMINATION OF BENZOIC ACID !
Purification of Organic Compounds:!

- Solids: Recrystallization!
- Liquids: Solvent Extraction!
- Solids and Liquids: Gas or liquid chromatography !

fluted filter paper: maximizes surfaces area =

faster filtration!

Short-stemmed funnel: lessen contact areas!

pre-heated receiving flask with minimum amount

Recrystallization in the Industry !

- used to manufacture the correct crystal size and

shape of a material. These factors can have a very

significant impact on how a medicine acts when
taken by a patient !
Benzoic Acid!
- usually additive in food & drinks!
- acts as preservatives > anti bacterial!
- insoluble in water: reacts with base !
- sodium benzoic acid > soluble !
Recrystallization !
- separate soluble solutes from a mixture of them in
solution!
- can be single solvent or mixed solvent process!
- a crystal is highly ordered assembly of molecules,
extending in 3 spatial dimensions !
- one of the most important method for purification of
solids !

General Steps in the Recrystallization of a compound!

1. Find a suitable solvent for the recrystallisation >
Solvent Selection!
most critical part!
Properties:!
- soluble in hot solvent, insoluble in cold solvent!
- impurities insoluble at all temperature with the
solvent!
- boiling point = low and lower than the melting
point!
- no reaction between solute and solvent!
- cheap, non-flammable & non-toxic!
Single Solvent (Water)!
Mixed Solvent !
- solvent pair:!
1st solvent - dissolves the crystals!
2nd solvent - poorly dissolves !
- two solvents must be miscible with each other !
- ethanol reacts with water > benzoic acids
appear (white powder/crystals)!
2. Dissolve the impure solid in a minimum volume of hot
solvent > Dissolving in Hot Solvent (Single & Mixed)!
Heat saturated solution with stirring!
excessive solvent = decreases % percent
recovery!
excess solvent will dissolve the benzoic acid >
no recrystallisation may happen !
small amount of charcoal = absorbed coloured
impurities !
Types of Impurities!
- soluble!
- insoluble!
- partially soluble!
- can be coloured !
3. Remove any insoluble impurities by filtration > Hot
Filtration !
removes insoluble impurities and prevents
premature recrystallization !

3.

4.

of hot solvent !
Slowly cool the hot solution to crystallise the desired
compound from the solution > Crystallization
Process!
rate of cooling and crystallisation affects the
crystal size and purity of the resulting crystals!
slow cooling = larger crystal = more pure!
- more time = more time to organize & remove
impurities = bigger crystals!
rapid cooling = smaller crystals = less pure !
- impurities may be trapped inside !
What do to if recrystallisation is a failure:!
- make the solution supersaturated by seeding
(a small crystal of the pure substance is added)!
- boiling off excess solvent!
- scratching the sides of the beaker !
Filter the solution to isolate the purified solid
compound > Obtaining the Crystal!
filtration !
wash with cold solvent !
dry !

Assessing the Purity: Melting Point Determination!

a pure substance has a fixed melting point while an
impure substance melts over a wide range of
temperatures and at a lower temperature than the pure
substance!
narrow range = high purity!
broad range = impure !

Consequence of Impurities!
The presence of impurities normally lowers the melting
point of a crystal as impurities defect the crystal lattice
and therefore reduce the energy (in the form of heat)
required to break the lattice bonds!

EXPERIMENT 3: EXTRACTION AND PURIFICATION OF

CAFFEINE!
Caffeine!
- Systematic Name: 1,3,7-trimethyl-1H-purine-2,6(3H,
7H)-dione!
- C5H10N4O2!
- Melting point: 238C!
- Sublimation point: 178C!
- belongs to a large class of organic compounds called
alkaloid !
- 1 nitrogen is basic > not part of another group!
- binds with adenacine thats why we do not feel
sleepy after drinking coffee!
- uses:!
treats migraine!
increases the potency of analgesics !
relives asthma attacks !
Caffeine Sources!
- coffee, coffee decaf!
- tea!
- cocoa, milk chocolate!

- baking chocolate!
- coca-cola!
Other Components of Coffee!
- lignin: gives the coffee its dark color!
- many acids: nicotinic acid, Quinic acid &

maintains basic pH = minimizes the caffeine lost!

washing with water: removes the remaining tannin
4.

hydroxycinnamic acid!

- water soluble > water cannot be used alone for

extraction !

Other components of Tea!

- chlorophyll, cellelose, common flavanoids, tannic
acid !
Solvent Extraction !
the method of separating a substance from a mixture by
dissolving one or more of the components in a solvent!
use 2 solvents!
- 2nd solvent: to get the compound that you need!
Solvents:!
- Non-toxic!
- Easily removed!
- Desired constituent is soluble!
- Non-reactive !
General Procedure!
1. Solid-Liquid Extraction !
Solvent: water!
Cellulose, caffeine, chlorophyll, tannins,
flavonoids extraction with H2O (100C)!
- H20 insoluble > extracted leaves = cellulose!
- H2O soluble > Aqueous tea solution =
caffeine, chlorophyll, tannins, flavonoids !
Basic nature of caffeine!
- N: more soluble if protonated!
- caffeine bound to tannic acid > we remove
tannic acid by reacting this with a strong acid
so that only the caffeine will remain !
- more soluble in nonpolar solvent!
- more soluble in water !
Removing Tannins!
- another way: add Ca(OH)2 or CaCO3!
- basic form of caffeine predominates!
- Ca(OH)2 reacts with tannic acid !
2. Liquid-Liquid Extraction !
Solvent: Dichloromethane!
used for separation of complex mixtures by
selective partitioning between two phases,
between two immiscible liquids !
Aqueous solution of caffeine, tannins, chlorophyll,
flavanoids PLUS 20mL dichloromethane!
- Organic Layer: Caffeine, impurities of
chlorophyll & tannins!
- Aqueous Layer: Hydrolyzable and nonhydrolyzable tannins, chlorophyll, flavanoids !
organic layer not always on top > it depends on the
density of the solutions!
drop test: adding of water > which layer adds,
thats the aqueous layer!
how to remove pressure: shake, tilt & remove the
pressure quickly !
3. Liquid Washings!
NaOH and Water!
washing with NaOH: removes remaining
impurities!

5.

salts and water soluble impurities !

Drying!
Crude Caffeine!
drying the organic layer = removing traces of
water!
by adding an insoluble inorganic solid to the
solution which will absorb the water, this drying it!
drying agents, should not be dissolved in the
solvent they are drying and easy to recover !
to decant easily!
drying agent > calcium chlorite !
Purification by Sublimation !
can be used if the vapor pressure of the impurities
in a solid are significantly lower than that of a solid
sample!
the compounds sublimation point must be far
away from its melting point!
caffeines sublimation point: 178C!
Melting Point: 238C!
not all organic compounds can be purified by
sublimation !
sublimation: easy to do > not solvents used =
pure crystals !
- draw back: few crystals !
impurities should not sublime !
sublimation point must be lower than the melting
point !

Recrystallization vs Sublimation !
Recrystallization !
Procedure!
- tedious!
- involves many steps!
Applicability!
- wide array of compounds!
Percent Yield!
- high!
Percent Purity !
- low!
Sublimation !
Procedure!
- simple and easy!
- involves only 1 step !
- doesnt require solvents!
Applicability !
- limited compounds (only with sublimation point)!
Percent Yield!
- low!
Percent Purity!
- high (almost 100% purity)!

EXPERIMENT 4: PAPER CHROMATOGRAPHY!

Chromatography!
a technique for separating mixtures into their
components in order to analyse, identify, purify an/or
quantify the mixture of components!
separates the components of a mixture by their
distinctive attraction to the mobile phase and the
stationary phase !

Paper Chromatography Components!

Stationary Phase!
- water bound to the cellulose structure of the paper
fibers!
- where the solute is initially deposited!
- other stationary phase: !
silica (SiO2)!
Alumina (Al2O3)!
cellulos!
- in the experiment, paper is polar thus when the
solvent does not move it is in the stationary phase !
Mobile phase/Developing Solvent/ Eluent!
- usually a mixture of 2 or more solvents!
- carries the individual components a certain distance
through the stationary phase, depending on their
attraction to both of the phases!
- moderately volatile, cheap & relatively less toxic !
Developing Chamber!
Solute/Extract/Mixture!
Types of Chromatography!
Normal Phase!
- stationary phase is more polar than the mobile phase!
- what was used in the experiment !
Reverse Phase!
- stationary phase is less polar than the mobile phase !
Preparing the Chromatography Paper!
use pencil in marking the origin line & solvent font !
- no ink > it may join with the solvent!
spot should be small & concentrated!
for multiple spots, make sure each spot has enough
distance from other spot !
Developing Chromatogram!
the developing chamber must be pre-saturated with
solvent before putting the paper and closed during the
elution !
- saturated chamber = faster movement of the spots:
more efficient movement of the spots !
ensure that the spots are not soak with solvent !
Visualization of Spots!
UV light!
- aromatics!
Iodine Chamber!
- reacts with double bonds!
Reacting Reagent !
Rf: solvent dependent!
- Rf = distance traveled/distance of solvent!
Applications of Chromatography !
Isolation of Compounds!
Reaction Monitorung!
Mixture of biphenyl, benzoic acid, benzyl alcohol !

EXPERIMENT 5: ISOMERISM & STEREOCHEMISTRY !

Isomerism!
same molecular formula, different structure!
Isomers = isos & meros > made of the same parts !
Isomers!
Constitutional/structural isomers: different connectivity
of atoms!
Stereoisomers: different spatial orientation of atoms!
- conformational isomers!
- geometric isomers!

- optical isomers !
Constitutional Isomerism!
different connectivity of atoms!
different names!
different physical properties!
avoid drawing the same isomer twice !
Stereoisomerism!
different spatial orientation of atoms!
1. Conformational isomerism!
2. Geometric Isomerism!
3. Optical Isomerism !
Conformational Isomerism!
free rotation about C-C single bonds > adopt variety
of 3D shapes > conformations!
Conformations with higher potential energy > less
stable!
Conformations with lower potential energy > more
stable !
Same physical properties !
Wedge & dashes!
Seahorse!
Newman Projection !
- Staggered conformation - has steric strain due to
electron cloud repulsion!
- Eclipsed conformation - !

!!

EXPERIMENT 6: PREPARATION & PURIFICATION OF

AN ALKYL HALIDE!
Synthesis of Alkyl Halide!
often carried out by nucleophilic substitution of alcohols
due to the following advantages:!
- often inexpensive and readily available!
- Targeted placement of the halide group where the OH group was!
- usually produces only the desired major product !
Steps:!
- Separatory funnel: 10ml tertbutyl alcohol + 20 ml cold
concentrated HCL!
- Stand for 20 mins. Add 3-5 ml 6M NaCL!
- Note the aqueous and organic layer !
- Get the organic layer + solid NaHCO3 until bubble
formation stops!
- Get the organic layer + anhydrous CaCl2!
- Simple Distillation !
Reagents: Cold Concentrated HCl!
- Cold = to prevent the volatilization of product, to
reduce the possibility of side reactions (E1 and
condensation)!
- Excess = drives the reaction forward !
- Concentrated = small amount of HCl needed, ensures
HCl is in excess !

!!

EXPERIMENT 7: ALCOHOL, PHENOLS & EHTERS!

Alcohols!
no gaseous alcohols are known !
alcohols higher than C12 are solids & are insoluble in
water!
Branched vs Straight Chain > Boiling point!
Numerous uses!

Reactions of Alcohols!
Alcohol + Na metal > alkoxide + H2 (g)!
Williamson Ether Synthesis!
Substitution & Elimination!
Oxidation !
Combustion!
Condensation!
Lucas Test!
used to distinguish among primary, secondary & tertiary
water-soluble alcohols!
- secondary & tertiary alcohols react via SN1
mechanism with the Lucan reagent !
- primary alcohols react in a similar fashion except the
free cation is not generated, the substitution of SN2
type !
Reagent: concentrated hydrochloric acid & zinc chloride!
positive result: cloudiness, two immiscible layers!
Complications !
often observe competing elimination with heating!
carbocations can lead to rearranged products!
volatility of formed alkyl halide!
fresh: Lucas reagent!
Insolubility of alcohol in Lucan reagent > false positive!
The reaction time is lower if the proportion of reagent to
alcohol is smaller, or it the temperature is lower!
Experimental Results (Test solutions + Lucas Reagent)!
Ethanol = almost an hour = no !
Isopropyl Alcohol = 5-10 minutes, layers form !
Tert-butyl Alcohol = Layers form immediately !
Benzyl Alcohol = Layers form immediately !
Diethyl ether = No visible reaction !
Oxidation !
Primary and secondary alcohols give positive results
> formation of brown precipitate !
Experimental Results (Test Solutions + neutral KMnO4)!
Ethanol = Decolorization > brown precipitate!
Isopropyl Alcohol = Decolorization > brown precipitate!
Tert-butyl Alcohol = Purple Solution !
Benzyl Alcohol = Decolorization > brown precipitate!
Diethyl Ether = Purple solution !
Phenols!
Physical Properties!
Acidity of Phenols!
- more acidic (pKa>>10) than alcohols (pKa>>16-20)!
- less acidic than carboxylic acids (pKa>>5)!
- conjugation exists between an unshared electron pair
on the oxygen and the aromatic ring !
Effect of Substituent Groups on Phenols Acidity!
- Electron withdrawing groups enhance the acidity!
- Electron donating substituents decrease the acidity!
- More favored if EWGs are located ortho & para with
regards to OH group !
Experimental Results (Test solutions & pH)!
Phenol = 5!
Para-nitrophenol = 3!
Picric Acid = 1 !
naphthol = - !
Para-bromophenol = - !
trend (increasing acidity): Phenol < para-nitrophenol <
picric acid !
Complexation with FeCl3!

Phenol!
- orange to purple!
P-nitrophenol!
- Orange to wine red!
P-bromophenol !
- Orange to dark yellow!
n!
- Orange to apple green solution !
Bromination of Phenol!
Occurs via EArS mechanism !
Oxidation of Phenols!
Positive result: decolorization of solution + brown
precipitate!
most fruits contain polyphenolic compounds that are
enzymatically oxidised to form qionones !
Ethers!
diethyl ether did not decolonize the neutral
permanganate and bromine = inert > very useful as
solvent!
medical use: diethyl ether anesthetic !

EXPERIMENT 8: ALIPHATIC AND AROMATIC

HYDROCARBONS!
Physical Properties !
Saturated !
- C-C bond!
- inert towards most chemical reagents!
- Solubility class: I!
- Boiling & Melting point increases with increasing
molecular weight!
- Can either be solid, liquid or gas!
- Insoluble in water!
- Less dense than water!
Unsaturated!
- C=C or C=C bond!
- Presence of pi elections > more reactive!
- Solubility class: N !
- react with strong acids > conc. HCl, H2SO4!
- Almost same physical properties with saturated HCs
(ex: MP, BP)!
- More volatile, can exhibit different colours !
Experimental Results!
Hexane!
- liquid!
- colorless!
- insoluble!
- less dense than water!
Limonene!
- liquid!
- yellow!
- insoluble!
- less dense than water!
Benzene!
- liquid!
- colorless!
- insoluble!
- less dense than water!
Free-Radical halogenation !

!!
!

!!
!!
!!
!!
!!
!!
!

Halogenated Products!

Combustion!
exothermic react > source of heat and energy !
complete combustion !
incomplete combustion: produces carbon monoxide
(toxic for our body)!
Saturated hydrocarbon!
- blue or orange flame!
- clean!
Orange crystals = reacted!
Experimental Result!
Hexane!
- t-BuCl/AlCl3 = white to yellow crystals!
- Br2, light = light yellow to colourless!
- Br2 dark = Red-orange!
- KMnO4 = purple solution !
- Combustion = blue, non-smokey flame !

Unsaturated Hydrocarbons!
- Halogenation!
occurs via electrophilic addition !
Br & Limonene exposed in light > no reaction
> electrophilic cannot happen!
Limonene: free radical !

!!
!!
!!
!!!
!!
!!
!!
!

EXPERIMENT 9: RELATIVE RATES OF ELECTROPHILIC

AROMATIC SUBSTITUTION !
Aromatic Hydrocarbons!
Physical Properties!
- some are liquids at room temperature while others
are crystalline solids!
- most are non-polar (insoluble in water)!
- volatile!
- they have a characteristic odor!
- Solubility class: I!
Chemical Properties!
- Unsaturated, presence of ring structure!
- Chemically stable!
- Carcinogenic > planar !
Friedel-Crafts Reaction (Alkylation)!

!!
!!
!!
!!
!!
!

Combustion !
Experimental Results!
Benzene !
- t-BuCl/AlCl3 = white to orange crystals!
- Br2, light = smoky yellow!
- Br2, dark = red-orange!
- KMnO4 = Purple solution!
- Combustion = yellow, smokey or sooty !
Benzene and Aromatic Compounds!
a compound is considered aromatic if it has cycles and
conjugated double bonds with 4n+2 pi elections (where
n = 0,1,2)!

!!
!
Oxidation !
Baeyers test for unsaturation !
Alkenes to cis-diols (oxidation: syn-hydroxylation)!

Combustion!
most often, incomplete combustion of unsaturated
compounds occurs!
Carbon atom consumes more oxygen atoms than
hydrogen does !

Electrophilic Aromatic Substitution !

in order to enhance the rate of reaction and the
reactivity of aromatic compounds, strong electrophiles &
Lewis catalysts are used !

!!
!!
!!
!!
!

Substituent Effects!
Electron Donating Groups !
- activates the ring, ortho & para directors!

!!
!

!!
!
!!
!!
!

Electron Withdrawing Groups (EWG) !

- deactivates the ring, meta directors (except
Halogens)!

Experiment: EA Bromination !
Theoretical Result!
- aniline > phenol > acetanilide > para-nitrophenol >
benzene > chlorobenzene!
Bromination of Acetanilide: Role of Solvent!

!!
!!
!!
!!
!!

Role of Solvent!
acetic acid polarises Br-Br bond > increases the rate
of reaction !
cyclohexane - non-polarizing solvent > decreases the
rate of reaction