Solubility of Organic Chemistry SOLUBILITY & ACID BASE PROPERTY OF ORGANIC
Polar Solvent
• All the molecules of the solvent are dipoles
• Contains partially positive and partially negative ends.
• polar solutes dissolve in nonpolar solvents
“like dissolves like”
• When you place a polar solute to a polar solvent, the solute’s
charges will match up with the charges of the solvent.
• SOLVATION – the solute is solvated by the solvent.
Non-Polar
• No dipoles.
• No partially positive and negative ends.
• For unlike, the strong attraction of the solvent to itself will not
let the non-polar solute in. It is simply expelled.
• non-polar solutes dissolve in nonpolar solvents
Solubility
• Fat in the Body
• Fatty Acid Chain
• Micelle
• Forms spontaneously due to solubility rules
o Long carbon chains in the molecule makes it
hydrophobic (water hating)
o OH groups outside the molecule makes it
hydrophilic (water loving)
COMPOUNDS
MOLECULES AND IONS
• Atoms – at ground state and are not charged
• Atoms when energized can form stable covalent bonds either
by equal (affected by electronegativity) or unequal sharing of
electrons.
o Non-polar Covalent bonding = Equal sharing of
electrons
o Polar Covalent Bonding – electronegativity
difference > 0.4; unequal sharing of electrons
• Ions – can either give (cations) or take (anions)
• The interaction between a cation and anion is an
electromagnetic force to form ionic compounds.
Solutions
• Homogenous mixtures – One Phase
• Can be Solid, Liquid or Gas
Water
• Universal Solvent
• Can dissolve Polar and Semi-Polar Compounds
• Ionic compounds are hydrated by water in order to dissolve.
o Negative Ion is surrounded by water
• Can dissolve organic compounds (Sugar)
o Sugar molecule is solvated.
SOLUBILITY
• Solubility is defined as the maximum amount of a substance
that will dissolve in a given amount of solvent at a specified
temperature.
o Unsaturated – dissolved solute is below saturated
point. More can dissolve. (Less)
o Saturated – dissolved solute is at saturated point.
No more can dissolve. (Maximum)
o Supersaturated – dissolved solute Is above
saturated point. Additional solute gathers at the
bottom. (Sobra)
How to dissolve?
1. Stir the solution to increase collision between molecules
2. If solute is solid, grind to fine powder to increase surface area for
contact with solvent.
3. May increase temperature for faster collision
§ Grinding – increases surface area for interaction.
§ Increasing Temperature – increases collisions.
SOLUTE & SOLVENT
• Solute – Is a chemical in smaller amount to be put in solution
like in a liquid of greater amount, to form a homogeneous
mixture. It is distributed equally in the solvent.
• Solvent – is the chemical in greater amount in a solution to
which the rest of the chemicals are distributed or dissolved to
form the homogeneous mixture.
The general rule in General Chemistry:
“like dissolves like”
Intermolecular forces of attraction (IFA) plays an important role in
solubility. Some IFA we encounter:
1. Ion-dipole interaction
2. Dipole-dipole interaction
3. H-bonding
4. Van der Waals interaction
Electronegativity - a measure of the tendency of an atom to attract a
bonding pair of electrons.
• Salts are hydrophilic while Oils are hydrophobic
FUNCTIONAL GROUPS IN ORGANIC CHEMISTRY Line Bond Structure
• Every end of a line is a carbon
R – chain of carbons
INTERACTION OF WATER WITH ORGANIC COMPOUNDS IT CAN
Hydrocarbons – made up of carbon and hydrogen HYDROGEN BOND WITH
• Alkane
o Single bonded sp3 Compounds that can form hydrogen bonds and can interact with
o Nonpolar water
o Inert – no reaction • Containing -OH groups
o No functional group • Phenol – aromatic with OH
o Fuel • With NH (Amine, Arene, Amide)
• Alkene
o Double bond sp2 Ethanol (2 Carbons)
o Reacts to become single bonds • The alcohol group in the ethanol can interact with water via its
o Unsaturated hydrogen donor.
• Alkyne • At the same time, the oxygen from the alcohol can accept
o Triple bond sp hydrogen proton from water.
o Unsaturated
• Arene Methanol (1 Carbon)
o Aromatic hydrocarbons • very soluble in water
• polar
Simple Oxygen Tetravalent (divalent – 2 bonds)
• Alcohol Butanol (4 Carbons)
o Hydroxyl group (-OH) • slightly soluble in water
• Ether • polar
o Singly bonded to two R
o Usually used as a solvent Octanol (8 Carbons)
• Epoxide • very insoluble in water
• nonpolar
Carbonyl Compounds (Carbon Double Bond groups, C=O)
• Aldehyde GENERAL RULE (IN WATER):
o Attached to Hydrogen • 4,3,2,1 Number of Carbons, Alcohols are POLAR
• Ketone • 5 and above carbon alcohols are NON-POLAR
o Attached to chain of R left and right • Solubility decreases as number of Carbons Increases
• Carboxylic Acid
o Attached to hydroxyl (OH) In Biological Systems
o E.g. Acetic Acid
• Acid Anhydride Water, the biological solvent (Biological Systems are 60% Water)
o Two carbonyls attached to oxygen • Biological organic molecules, in order to maintain water-
o Sandwich oxygen center solubility, contain one or more charged functional groups such
• Ester as phosphates, carboxylates, ammoniums
o Carbonyl attached to oxygen • Some compounds have to be miscible in water/interact with
o Attached to chain of carbon water.
• Amide • Those with ion charges can interact with water.
o Attached to carbonyl group and amino group
(NH2) NOT BASIC Dipole-Dipole Interactions
• Acyl Halide • There are two poles; Partial positive and Partial Negative
o Carbonyl group attached to a halide • Dipoles are created by differences in electronegativities
between nearby atoms
Nitrogen Based • Interactions between opposite-charged dipoles are attractive
• Amine • Similar in origin to hydrogen bonding, but since the differences
o Attached to amino group in electronegativities are smaller
o Most Basic Compound
• Nitrile Van der Waals
o Contains triple bonded Nitrogen • Equal sharing of electrons
• Imine • Momentary partial positive or negative interactions
o Double bonded nitrogen
Sulfur Based GENERAL SUMMARY:
• Haloalkane
o Attached to a halogen

Chemist’s Shortcut in Drawing structures:

A single bond is represented with a single line. A double bond is shown
by two parallel lines, and a triple bond by three parallel lines. The
position of carbon atoms may be shown with letters, or may be implied
(in certain circumstances)

Structural Formula
• Shows all the bonds and atoms in the compound
as you increase number of Carbons, polarity decreases
Condensed Formula Non-Polar: hydrocarbons
• Grouped Semi-Polar: Ethers, Esters, Halides, Ketones, Aldehydes
• Functional group is not combined Polar: Amines, Alcohols, Acids
But also recall that number of carbons also affect the polarity.
Orientation: Sulfuric Acid is soluble in:
Compounds with oxygen
• Esters
• Alkenes
• Alcohols
• Ketones
• Aldehydes
• Anhydrides

Sulfuric Acid is not soluble in:

• Alkanes
• Alkyl halides
• Aromatic hydrocarbons
• Aryl halides

SOLUBLE WITH H2O

• Small (1-4) carbons
• Amines
• Carboxylic Acids
• Alcohols
• Aldehydes
• Ketones
• Ethers
• Esters
• Amines

Highly polar big molecules with many hydroxyl groups (polyhydrate)

like glucose and sucrose are soluble in water.
e.g. Sugar

Soluble in Water:
• 4 carbons and less
• Low MW amines (RNH2)
• Low MW carboxylic acids
• Low MW neutral compounds
o All compounds with oxygen and nitrogen
o Aldehydes SOLUBLE WITH 5% NAOH
o Ketones
• are strong and weak organic acids.
o Alcohols
• it is 95% water.
o Esters
• An aqueous solution.
o Amides

Greater than 5 Carbons

NaOH BASE is Soluble in
Acidic Organic Compounds
o Carboxylic Acid (stronger)
o Phenols (Weaker)

NaHCO3
o Carboxylic Acids – YES
o Phenol – NO

HCl is soluble in:

• Amines - Carboxylic acid reacts with sodium hydroxide to form soluble salts
soluble in water.
HCl NOT soluble in:
Neutral compounds (neither acid or base)
• Aldehydes
• Ketones
• Alcohols
• Esters
• Amides
• Alkenes
• Anhydrides
SOLUBLE WITH 5% NAHCOS
• Strong acids react with salts of strong bases and weak acids ANSWER: C < B < A
(NaHCO3 à NaOH + H2CO3)
• Phenol will not react with Sodium Bicarbonate because it has A: Amine
a higher pka. B: Amine in a Benzene
Ring
C: Amide

ANSWER: C

A: Alcohol
B: Carboxylic acid
C: Salt – soluble in water!
Soluble with 5% HCl D: Alkane
• Amines – basic IF ACID LAHAT E: Aldehyde

Amines – Basic
Amides – Not Basic ANSWER: C
A: Alcohol
Aromatic – Less basic B. 6 carbons
Non-Aromatic - Basic C: 4 – OH making it soluble in
water
D: Inert
RECITATION: E: carboxylic acid

ANSWER: C ANSWER: D > B > A > C

REASON: Phenol is an acid
and Alcohol is a neutral
compound. NaOH can react
with a weak acid.

NaHCO3 cannot react with a

weak acid.

ANSWER: A KHAN ACADEMY

REASON: Number of Carbon
atoms
Solubility of organic compounds | Structure and
bonding | Organic chemistry |
Important:
• The number of carbons overcomes the properties of
functional groups!
• Many OH groups in a compound results in higher chances
ANSWER: B of hydrogen bonding, therefore making it polar in water
REASON: Left is Carboxylic • Pag may charge ung acid or salt siya, mas soluble siya in
Acid and Right is a Phenol. water.
NaHCO3 is used to differentiate
the two compounds.

ANSWER: A < B < C

A: Alcohol
B: Phenol
C: Carboxylic Acid
 PRE LAB: ORGANIC COMPOUNDS & FUNCTIONAL
REPORTING: GROUPS
GROUP #1
• There is a 109.5 degree angle between carbons (zigzag lines)

Shabu

• In the benzene ring, there are 6 carbons

• In the benzene ring, there are 5 hydrogens

• In the right side, there are 4 carbons

H2SO4 – Soluble to a Presence of Oxygen • In the right side, there are 10 hydrogens
GROUP #2

Wedge - front
Broken Line - back

FUNCTIONAL GROUPS

SATURATED

1. Alkanes (sp3 carbons)

Cyclohexene – Alkene is soluble to H2SO4
- no functional groups
- just carbons hydrogen single bond
- increasing the number of carbon enable it to become
Gas → Liquid → Solid
E.g. propane butane methane

UNSATURATED
1. Alkene (sp2 carbons)
- contains one or more carbon carbon double bonds
- sometimes called as “olefin”

2. Alkynes (sp carbons)

-carbon triple bonds
ARENES NITROGEN AND SULFUR CONTAINING
Aromatic Hydrocarbons
-benzene
1. Amine
-the double single double single bonds makes it aromatic
-6 carbons
- the R-Group is a carbon chain

CARBONYL GROUP (KETO-GROUP) • NH2 attached to a chain of carbon

• Fishy odor
1. Aldehyde • Cadaver

2. Nitrile

• Carbonyl added is attached to hydrogen

• E.g. Ethanal • Nitrogen forms triple bonds with carbon (sp)

2. Ketone
3. Imine

• An R group is attached to carbonyl

• Carbon double bond nitrogen (sp2)
• E.g. Acetone

4. Isocyanate
3. Carboxylic Acid

• Azo Compound
• Hydroxyl is attached to a carbonyl
• E.g. Vinegar 5. Thiol

4. Acid Anhydride

• Sulfur attached to Hydrogen

• Two carbonyls that sandwiches an oxygen in the center

• Less acidic than carboxylic acid
*THOROUGH EXPLANATION:
•
5. Ester
HYDROCARBONS
-contain only carbon & hydrogen

Alkanes (Saturated) C-H

• An alkoxy group (OR) is attached to the carbonyl • No functional group generally UNREACTIVE (Inert)
• Has distinct smell, fruity odor • Memorize up to 10 carbons!
• E.g. coconut oil

6. Amide

• Amino group is attached to carbonyl

• Link that makes up protein (polymer)
• Not Basic

7. Acyl Halide

Unsaturated
Alkenes
• Halogen is attached to carbonyl • Contains c-c double bonds
• used in synthesis
Alkynes
• Contains c-c triple bonds

*Unsymmetrical - if magkaiba ung R group sa left at right

 • Example 1: Toluene
The HYDROCARBONS o Ung hydrogen is the one which is oxidized to form
• The basic reaction that alkenes have is addition. carboxylic acid
o May dadagdag sa double/ triple bond; mawawala • Example 2: CH2 is oxidized to form carboxylic acid
ung double magiging single • Example 3: 2 CH2 is oxidized to form 2 carboxylic
o For triple bonds, magiging double then magiging • Example 4: No more CH since may 4 bonds na ung carbon
single sa gitna, therefore walang hydrogen na maooxizide = NO
REACTION
BROMINATION OF ALKENES o para siyang tertiary

HALOALKANES OR ALKYL HALIDES

• may halogens na
• Compounds are usually insoluble in water (cloudiness of
solution which indicates presence of haloalkanes)
Aromatics
• Contain carbon hexagon To classify alkyl halides, count the number of carbons connected to
• With 3 double bonds inside: called ARENE the carbon with the halogen atom.
• Not the same from alkenes
• There is an alternating double single bond which makes it
STABLE
• Ung magrereact sakanya is ung nakakabit na alkyl or carbon
chain
• Toluene smells like rugby

Nasa Experiment to!

FUNCTIONAL GROUPS WITH SINGLY BONDED OXYGEN (C-O)

ALCOHOLS
Carbonyl Carbon - A carbon where Hydroxyl is connected

*technique is invisible hydrogen attached to carbon

* count the number of carbons connected to the carbon with the
halogen atom.

• Primary Alcohol - 2 oxidizable hydrogen attached to carbon

• Secondary Alcohol - 1 oxidizable hydrogen attached to carbon
(e.g. Isopropyl Alcohol)
• The attached carbon chain are the ones that will react with
KMnO4 (an oxidizing agent) • Tertiary - no oxidizable hydrogen attached to carbon; resistant to
• Oxidation wherein it is an addition of oxygen oxidation
Youtube Video
EXERCISE: FERRIC CHLORIDE TEST
• Alcohols will not react with ferric chloride
• Phenols form a colored complex (complexation with iron) red
burgundy color

A GUIDE TO OXIDATION REACTIONS OF ALCOHOLS

Ethers - solvents WALA TEST

FUNCTIONAL GROUPS WITH DOUBLY BONDED OXYGEN (KETO

GROUP)

2,4-DINITROPHENYLHYDRAZINE TEST (DNPH TEST)

Test for Aldehydes and Ketones
• Only aldehydes and ketones will react with dinitrophenylhydrazine
test
• Gives a color yellow to red precipitate.

ALDEHYDES
• will react with dinitrophenylhydrazine test (DNPH Test)

-Primary and Secondary alcohols are oxidizable.

- Primary alcohols can be oxidized to aldehyde first due to a hydrogen
attached to the carbonyl. Then hydrogen of aldehyde is oxidized to
carboxylic acid.
- Secondary alcohols has only one hydrogen oxidized to ketone.

JONES TEST
• Can differentiate primary and secondary from tertiary alcohols.
• Tertiary alcohols does not react with jones test.
• Be careful with structure! Medyo nakakalito

LUCAS’ TEST
TOLLEN’S TEST (FOR ALDEHYDE)
• Differentiates tertiary alcohol from primary alcohol
• Very sensitive
• Reacts with tertiary alcohol
• Gives silver metal for aldehydes (silver mirror deposit)
• Reacts at once with Lucas reagent (HCl & ZnCl2)

• If sobra ung lagay ng silver nitrate, walang makukuha na positive

• Hydroxyl is replaced by a halogen making to compound insoluble result.
in water (Cloudy/Turbid solution) • Silver(I) is reduced by the aldehyde, forming atomic silver, which
forms a mirror on the reaction flask.
Phenols
• Not alcohols Ketones
• The hydroxyl is attached to an aromatic ring. - Does not react with Tollens’ Test
• Ferric Chloride Test for Phenols.
IODOFORM TEST Experiment 2B: Characterization of Hydrocarbons
Iodoform Reaction is an Indicator specifically for methyl carbonyl
(yelloe precipitate) Nitration Test
• Specific for methyl carbonyl Differentiates Aromatics (+) from Aliphatic (-)
Reagent used: Concentrated Nitric Acid & Concentrated Sulfuric Acid
(1:1) Ratio
Positive Result: Yellow Globule
Result
Hexane Transparent solution with the
formation of an oily layer ( -
result)
Cyclohexene Transparent solution with the
formation of an oily layer ( -
solution)
Toluene Yellow Globule/Oily Layer (+
result)
Benzene Yellow Globule/Oily Layer (+
result)

Reaction
Hexane No Reaction
Cyclohexene No Reaction
Toluene

• Looks for the presence of Iodoforms

Carboxylic Acids
• Solubility test
• NaHCO3 can differentiate
Benzene

Esters
• Hydroxamic acid test
• Type of Reaction: Electrophilic Aromatic Substitution
Reaction (Electrophile – electron loving)
• Aromatic is very stable so hindi siya nasisira
• Umiikot ang electrons sa Aromatics (No sharing); it can
substitute the hydrogen attached para kumabit ung NO2 in
any of them.
• NO2 – is the yellow globule formed.

Amides
• Wala Bromine Test
Presence of Unsaturated hydrocarbon
Reagent used: 2% Bromine in dichloromethane solvent
Amines Positive Result: Immediate Decolorization
• Solubility test Hexane Reddish Brown ( - result)
• Reactive with HCl to form salt Cyclohexene Colorless Solution ( + result )
Toluene Reddish Brown ( - result )
SECONDARY LITERATURE Benzene Reddish Brown ( - result)
• Publications that parse, abstract, index, or otherwise break down Reaction: Anti-Addition – wherein one bromine is wedge (front) while
and group the information and ideas appearing in the primary the other one is broken line (back).
literature are categorized as secondary literature
• Examples are handbooks, textbooks, Book of Abstracts, Safety
Data Sheets
Baeyer’s Test (Alkaline Potassium Permanganate)
Due to the presence of OH-
Presence of Unsaturated and Alkyl Substituted Aromatic Ring
Reagent used: 0.1% alkaline potassium permanganate (alkaline:
NaOH)
Positive Result: Brown Precipitate in a Violet Solution

Result
Hexane The pinkish, purple coloration of the 0.1% alkaline
potassium permanganate remains unchanged.
( - result)
Cyclohexene Brown ppt. in clear solution ( + result )
Toluene Brown ppt. in clear solution ( + result )
Benzene The pinkish, purple coloration of the 0.1% alkaline
potassium permanganate remains unchanged. (-
result)
Reaction
Hexane No Reaction Nag open pa ung Benzoic Acid (from Baeyer’s) to form a carboxylic acid
Cyclohexene Toluene

Toluene

*Presence of Salt
Benzene No Reaction
Reaction: Oxidation Reaction (RedOx Reaction)
• Reduction of Mn+7 which was responsible for the alcohol
result. (Mn+7O2 à Mn+4O2; brown precipitate)
• The product underwent oxidation forming an alcohol.
Benzene No Reaction
Reaction: Redox Reaction
There is an additional oxidation of sulfuric (oxidizing agent).
• Mas malakas na oxidizing agent kasi may sulfuric acid kaya
mas malayo reaction pagdating sa cyclohexene
Question:
If the reactant is tert-butylbenzene (C10H14) or (1,1-dimethylethyl)
benzene.
What do you think is the reaction with KMnO4?

Answer: No Reaction due to no presence of oxidizable hydrogen.

Additional Notes:
• Warm water bath is used in order to speed up the reaction.

Experiment 2B: Characterization of Oxygen Bearing

Organic Compounds

Summary:
Positive Results of the following compounds:

A. Ethyl Acetate
• Hydroxamic Acid Test

B. Methanol
• Jones Test
• Ceric Nitrate Test

C. 2-propanol
• Jones Test
• Iodoform Test
• Lucas Test
• Ceric Nitrate Test

Tests:
Acidic Permanganate Test 1. Dichromate Test (Jones Test)
Presence of Unsaturated and Alkyl Substituted Aromatic Ring Positive Result: Dark green colored solution
Reagent Used: 0.1% potassium permanganate KMnO4 and 10% - Used to identify Primary and Secondary Aliphatic Alcohols.
Aqueous H2SO4 - Reaction undergoes oxidation.
o Primary Alcohol à Aldehyde à Carboxylic Acid
Result
Hexane Purple solution( - result) o Secondary Alcohol à Ketone
Cyclohexene Brown ppt. in clear solution ( + result )
Toluene Brown ppt. in clear solution ( + result ) Reagent: Orange Solution
Benzene Purple Solution ( - result) 10% M Aqueous K2Cr2O7 and (5 drops)
6M H2SO4 (5 drops)
Reaction
Hexane No Reaction Reaction: RedOx
Cyclohexene
2. DNPH Test
Positive Result: orange-yellow precipitate
- Used to distinguish alcohols/esters (unreactive) from aldehydes and
ketones.

Reagent: DNPH Reagent (2,4-Dinitrophenylhydrazine) composed of:

 • 3g DNPH Results:
• 15 mL conc. H2SO4
• 20 mL H2O A. 1o ROH (Methanol)
• 100 mL Ethanol

Reaction: Substitution Reaction

3. Iodoform Test
Positive Result: yellow precipitate
- Determine the presence of an Indicator specifically for methyl
carbonyl attached to an aldehyde or ketone.
- Yellow precipitate
Positive Result:
• Dichromate Test (Jones Test) – dark green colored solution
• Ceric Nitrate Test – red colored solution

Reagent: 10% Aqueous KI solution and (10 drops)

5% Aqueous NaClO solution (Chlorox) (10 drops) B. 2o ROH (2-Propanol)

Reaction: Oxidation Reaction

4. Hydroxamic Acid Test

Positive Result: red solution
- Only reacts to esters.
Positive Result:
• Dichromate Test (Jones Test) – dark green colored solution
Reagent:
• Iodoform test – yellow precipitate
• 1% ethanolic hydroxylamine hydrochloride 5% ethanolic (5
• Lucas Test – Cloudy Layer
drops)
• Ceric Nitrate Test – Red complex
• 5 % FeCl3 solution (2 drops)
• 3M NaOH (5 drops)
C. 3o ROH (tert-Butanol)
• 3M HCl (10 drops)

Reaction: Substitution Reaction

5. Lucas Test
Positive Result: Tertiary – immediate cloudiness
Secondary w/ heating – cloudy
Positive Result:
Primary – No Reaction
• Lucas Test – cloudy layer (turbidity)
- Differentiates the presence of a tertiary alcohol from a primary
• Ceric Nitrate test – red complex
alcohol.
- Reactive to tertiary alcohols in 5-10 minutes.
Reagent:
D. Aldehyde (Formaldehyde)
• Lucas Reagent (10 drops)
o 27 g anhydrous ZnCl2
o 18 mL conc. HCl

Reaction: Substitution Reaction

Positive Result:
6. Tollens’ Test
• DNPH Test – yellow precipitate
Positive Result: Silver Mirror Solution
• Tollens’ test – black precipitate
- Distinguish an aldehyde from a ketone.
- Reacts to only carbonyl groups (C=O)
E. Ketone (Acetone)
Reagent:
• Tollens Reagent (Ammoniacal Silver nitrate) (20 drops)
o Freshly prepared and used because may result to
explosive precipitate
o 0.25 g AgNO3
o 0.3 g NaOH
Positive Result:
o 8.5 mL H2O
o Conc. NH3 • DNPH – orange-yellow precipitate
• Iodoform Test – yellow precipitate
Reaction: RedOx Reaction

7. Ceric Nitrate Test F. Ester (Ethyl Acetate)

Positive Result: red solution
- Determine the presence of alcohols (red indicator)

Reagent:
• Ceric Ammonium Nitrate Reagent
o 45 g Ce(NH4)2(NO3)6 Positive Result:
o 115 mL 2M HNO3 • Hydroxamic Acid test – deep red solution
Reagent List: 3. Crystallization and Recrystallization (Purification Techniques)
4. Filtration
Jones Test (dichromate 10% M Aqueous K2Cr2O7 &
test) BOILING POINT
DNPH Reagent (2,4- • The temperature at which the vapor pressure of the liquid equals
DNPH Test
Dinitrophenylhydrazine) the atmospheric pressure.
10% Aqueous KI solution & 5% • Characteristics: vigorous bubbling and agitating of the liquid
Iodoform Test (churning)
Aqueous NaClO solution (Chlorox)
• 1% ethanolic
hydroxylamine
hydrochloride 5% ethanolic
(5 drops)
Hydroxamic Acid Test • 5 % FeCl3 solution (2
drops)
• 3M NaOH (5 drops) • A liquid boil when it is able to overcome its atmospheric pressure.
• 3M HCl (10 drops) • Temperature is seldom reproducible because of impurities and
superheating.
Lucas Reagent • In distillation, the temperature of boiling is always higher than
• 27 g anhydrous ZnCl2 temperature of distilling liquid.
Lucas Test
• 18 mL conc. HCl TBoiling > TDistilling
• In distillation, the temperature is measured above the surface
Tollens Reagent (Ammoniacal Silver where vapor and liquid are in equilibrium.
nitrate) • Boiling is reported as a range. A pure compound exhibits a range
• 0.25 g AgNO3 of 1o-2. Boiling points vary with changes in applied pressure.
Tollens’ Test • 0.3 g NaOH
• 8.5 mL H2O
• Conc. NH3 Ideal Liquid Mixture:

Ceric Ammonium Nitrate Reagent • In an ideal liquid, a

• 45 g Ce(NH4)2(NO3)6 homogenous mixture with
Ceric Nitrate Test
• 115 mL 2M HNO3 no intermolecular
interaction, the low
boiling liquid can be
Reaction List: collected in one flask, the
Jones Test (dichromate test) RedOx higher component in
DNPH Test Subtitution another flask, while the
Iodoform Test Substitution highest boiling component
Hydroxamic Acid Test Oxidation remains in the distilling
Lucas Test Substitution flask.
Tollens’ Test RedOx • Miscible and No IMF
Ceric Ammonium Nitrate Test • Affected by Dalton’s Law and Raoult’s Law

Dalton’s Law of Partial Pressure

• total pressure of a gas is the sum of the partial pressures of its
individual components.
PRE-LAB: EXPERIMENT 3A AND 3B
DISTILLATION, SALTING OUT AND DRYING PTOTAL = PA + PB
Raoult’s Law
2 MAJOR TECHNIQUES: • the partial vapor pressure of a compound in an ideal solution is
equal to the vapor pressure of that pure compound multiplied by its
1. Distillation mole fraction in the liquid
• Separation technique
• Mixture / Solution (Homogenous) which involves differences in PT = PoAXA + PoBXB
boiling points of liquid components.
• May nauuna na mag evaporate & condense due to low boiling point Liquid Phase
and may naiiwan na w/ high boiling point.
• A common Organic Chemistry technique used for
1. Removing a solvent
2. Purifying a liquid
3. Separating the components of a liquid mixture
• In distillation a liquid is vaporized by boiling then condensed back
to liquid called the distillate or condensate.

2. Reflux
• Heating method
• We need to heat to cause the reaction.
• Prevents the loss of reactants by condensing.

• Both techniques involve Evaporation and Condensation

Minor Techniques • Line – liquid composition

1. Salting Out – Extraction Technique • As temperature rises, some of B evaporates (but not all) until all of
2. Drying B evaporates leaving only pure A.
• You will never get pure B at the beginning because it is a mixture.
• As you increase the temperature, you increase the concentration Efficiency of the Fractionation Column
of the high boiling component. • Efficiency – how well a fractionation column can separate a pair
of compounds.
Vapor Phase • Depends on
• when the liquid boils, the liquid is in o (1) length and packing. The greater the length
equilibrium with the vapor. the more efficient. Same length but greater surface
area increase efficiency.
o (2) Reflux ratio, ratio of the amount of material in
the distillation head that undergoes reflux,
condensing and flowing back onto the column to
the amount of material removed through the side
arms as distillate.
• Efficiency of the column is reported in theoretical plates.

C. Steam Distillation
• Introduces steam that causes mixture to become immiscible
Azeotropes • Components that are immiscible w/ water (like oil) distills at a
temperature lower than water.
• Laws do not apply! (Raoult’s and Dalton’s Law)
• Are mixtures, that due to • The High Boiling point component boils at a lower temperature than
intermolecular forces of attraction, water.
such as H-bonding, do not follow o e.g. extraction of oil in plants
Raoult’s Law. • Co-distills with water at a lower temperature.
• Are mixtures that distill at a
constant boiling point like pure • Is the distillation of a mixture of water (steam) and an organic
compounds. compounds or a compound or a mixture of organic compounds.
• They behave like pure liquids. • The organic compound must be immiscible in water thus do not
behave like solutions.
• The components of the immiscible mixtures boil at a temperature
• The low boiling point on the graph ,b, represents the azeotropic lower than the boiling points of any of the components.
mixture. • Components thus can be distilled at a temperature lower than
• Is lower than that of either pure component 100oC.
• The azeotrope will distill before a component present in excess • Flavorings and perfumes from plants can be separated by steam
distillation.
• The pure compound in excess will distill after the azeotrope has
completely distill
D. Vacuum Distillation
• Some azeotropes have boiling points intermediate between those
• Lowers atmospheric pressure therefore;
of their components while others have higher boiling points than
• Liquid boils at a lower temperature
the components.
• Used for heat sensitive materials. (Biological samples)

• Is distillation under reduced pressure.

TYPES OF DISTILLATION: • When the pressure over a liquid is reduced, the liquid boils at a
lowered temperature.
A. Simple Distillation
• Vacuum distillation is used for distilling high-boiling or heat-
• Purification of a volatile compound with little or no volatile sensitive compounds.
impurities.
• For compounds that do not decompose on heating. SETP UP:
• when liquid component is volatile w/ a non-volatile. A. Simple Distillation
• liquid mixture with components of 75-100o C differences.

B. Fractional Distillation
• separate liquids with ~30oC Bp difference
• fractionating column wherein several simple distillation is
happening in that column
o Fractionating column has a packing materials
§ Glass beads, Cylinders, Glass, Metal
Sponge, Steel wool
§ Improves Separation components that
increases surface area where
evaporation & condensation occurs
(Simple Distillation)
• As vapor rises through this column, It condenses the packing and
revaporizes continuously. each revaporation-condensation is
equivalent to a simple distillation known as theoretical plate.
• Steel head – connector that connects thermometer; has a side
arm
• Do not immerse the thermometer, it can cause erroneous results.
(overheating)
o Place it wherein liquid and vapor are in equilibrium
In Condenser:
• Water inlet – cools down condenser Water outlet – water goes
out
• Collector – for distillate
• Residue – natira in first flask
 • You are heating up to cause the reaction but you do not lose the
B. Fractional Distillation reactant.
• There is a presence of a fractionating column with packing material.
o Vigreux – tinik-tinik SALTING OUT
• Theoretical plates – equivalent to several simple distillation => • Is an extraction technique using a Separatory Funnel
more efficient.

• The separatory funnel has a stop cock.

• There are two immiscible liquids.
• The addition of water causes immiscibility.
C. Steam Distillation
• A source of steam is connected to distilling flask.
o Organic Layer
• 2 neck distilling flask needed. o Water Layer
• A saturated NaCl is added so that the organic compound is
displaced from the aqueous layer. Malilipat lahat ng organic
component sa organic layer.

• Is used if a compound has allow distribution between an organic

solvent or water
• The distribution coefficient of an organic compound between
organic solvent and water can be changed by adding chloride to
water.

steam distillation that allows water to be added during distillation DRYING AFTER EXTRACTION

C. Vacuum Distillation
• Vacuum source is introduced to cause vacuum.
• 2 neck distilling flask
• Note: Let some air in to prevent bumping (rise)
• Has a fractionating column.
• SEALED

• Using anhydrous salts to adsorb water residues.

anhydrous à hydrated (colloid)
• To ensure that there is no residual water.
• Removing of residual water after extraction using anhydrous salt
• Common drying agents are anhydrous inorganic salts that acquire
waters of hydration when exposed to moist air of a wet solution. For
the most common drying agent such as sodium sulfate or
magnesium sulfate, the crystals form large chumps when they
absorb water.

Rot-evaporator • Anhydrous becomes colloidal if kulang ung nilagay na salt. Add

• Often used to remove a solvent from heat sensitive material and until crystals na ung colloid.
recovering the solvent. • To remove:
o Decantation – decantation (Decante)
REFLUX o Filtration – using filter paper (Filtrate)
• Heating method to cause a reaction.
• Do not directly heat (use hot water bath). Lalo na if less than 100oC. FILTRATION
• Gravity Filtration – Fluted filter paper vs. Cone Filter paper
• Vacuum Filtration – Büchner Funnel w/ Filter Flask

3A: SIMPLE DISTILLATION, SALTING OUT &

DRYING

VIDEO #1. Fractional Distillation ✓

• Used for the separation of 2 or more liquids whose boiling point

differ less than 75o
• Distilling flask should be raised off the bench top, sitting on a
• Pabalik balik sa distilling flask. wooden block or iron ring.
Use of Fractionating Column • An ice bath and small additions of red phosphorus was made in
• adds surface area which increase the # of vaporizations / order to prevent the methyl iodide from being synthesized to
condensations results to multiple vaporization and immediately evaporate since the reaction may exceed
condensation (Theoretical Plates) temperatures of 42 degrees Celsius.
• Ex. Vigreux Column – lots of cool indentations (6-10
Theoretical Plates) Reaction:
§ Make sure there is a stir bar or boiling stones in the distilling flask 1) Product is extremely reactive and reacts immediately to methanol in
§ Bulb of thermometer should be below the side arms to accurately eqn. 2.
determine boiling point.
§ Water input should be at the bottom and outlet at the top.
§ Do not directly plug your heating mantle to the outlet. Use a variant
control.

VIDEO #2. Carrying out a Steam distillation ✓ 2) Substitution Reaction

• Used to extract natural oils from plant material.

• Water is added to distillation flask to approximately half the flask
before heating the flask.
• A 2 neck round bottom flask is used to add a dropping funnel
to add more running water as the distillation procedure is done. Overall Reaction:
• A stopper is used to block the second head of the steel neck since
a thermometer is not used.
• During experiment, add small portions of water from the dropping
funnel in order to maintain the level of water throughout distillation.
• Distillate – water and oil.
• How to know if distillation is done: when no more oil is visible in
the distillate.

VIDEO #3. How Steam Distillation Works ✓
• 1000 AD by Avicenna
• Dried plants extraction into pure essential oil.
• Limbic Chamber – Holds the plant material, Biomass (which
contains essential oils in sacks)
• As steam is delivered to biomass, the temperature causes the
sacks burtst open releasing the essential oils.
• The oil and steam rise and pass through a tube to the cold
condensing chamber.
• Water – hydrosol
Experiment 3A: Synthesis of Methyl Iodide
Methyl Iodide (CH3I) – Carbon and Iodide bond is not very strong and
can be broken.
Reaction Mechanism:
• Simple Distillation at around 70o in a warm bath.
• Aluminum foil is wrapped to prevent methyl iodide from condensing
on the walls of the round-bottom flask.
• Receiving flask is cooled with an ice bath to limit the evaporation of
methyl iodide.
• If temperature starts to rise above 42o, STOP.
• Distillate: Methyl Iodide contaminated with Iodine (faint yellow
color)
• Residue: Red Methanol sol’n and Red Phosphorus (solid)
Sorting Out / Salting Out
• Addition of 60 mL sat. NaCl with a bit of Sodium thiosulfate
Iodine (Yellow) à Instant Decolorization
• Sodium Thiosulfate reacts with Iodine to form colorless sodium
Iodide.
• NaCl separates the denser liquid from less dense. Displaces the
organic compound.
• Bottom layer is the one collected – Colorless sodium iodide.

Drying out
• CaCl2 drying agent added to dry out any methanol or water that
remained.
Cloudy à Clear

Filtration:
• Calcium chloride was added in order to react with the remaining
traces of water and methanol existing within the solution. The
calcium chloride was then being filtered out by the cotton, leaving
Materials: behind only the pure methyl iodide.
! 83.3 g Iodine (I) • Copper (polished) helps to prevent to break down due to presence
! 42.3 g Red Phosphorus (𝑃4) of light. Sensitive to light. It would be best to wrap it with aluminum
! 120 mL methanol (𝐶𝐻3𝑂𝐻) foil.
! 60 mL sat. NaCl solution (𝑁𝑎𝐶𝑙𝑠𝑎𝑡.)
! A few crystals of sodium thiosulfate (𝑁𝑎2𝑆2𝑂3) Recovery of Red Phosphorus:
! Calcium Chloride drying agent (𝐶𝑎𝐶𝑙2) • Filtration
• Use of Vacuum
Method: • Washed with dilute sodium thiosulfate solution to get rid of any
• Add 120 mL methanol iodine remains.
• Add 83.3 g Iodine. The moment it is added, it completely
dissolves and becomes a clearly black color.
• Washed with water and methanol.
• Add sitr bar. • Final Washing – Vacuum
• The small addition of Red Phosphorus will initiate the reaction and • Leave in Air to dry
the production of methyl iodide. Exothermic reaction (releases
heat).
 REFLUX, CRYSTALLIZATION & VACUUM FILTRATION
3B – WILLIAMSON ETHER SYNTHESIS OF
PHENACETIN
Recrystallization – most common method used to purify solids.
- A compound formed in a chemical reaction or extracted from some
natural source is rarely pure when initially isolated.
Contaminants:
Side reactions, Unchanged starting materials, inorganic materials, and
solvents
ONE SOLVENT SYSTEM OF RECRYSTALLIZATION:
• dissolving the solid in an appropriate solvent at an elevated
temperature and allowing the crystals to re-form on cooling, so that
any impurities remain in solution.
• abrupt cooling traps impurities.
• Vacuum filtration used to isolate purified solid.
STEPS:
1. Selection of an appropriate solvent – ethanol/water
2.Dissolution of the solid to be purified in the solvent near or at its boiling
point.
3. Decoloration with Na2S2O4 (based from our exp) or activated carbon,
if necessary, to remove colored impurities, and filtration of the hot
solution to remove insoluble impurities and the decolorizing salt.
4. Formation of crystalline solid from the solution as it cools.
6.Drying the crystals.
TWO SOLVENT SYSTEM OF RECRYSTALLIZATION: ETHANOL/WATER
• First Solvent: added hot to dissolve (soluble)
• Second Solvent: added to boiling solution until cloudy (less
soluble)
• Cloudiness – signals initial formation of crystals
• Failure of crystallization after cooling means that too much solvent
has been used.
• Crystallization can be induced by using a glass rod to rub the inside
surface of the crystallization vessel at or just above the air-solution
interface.
• Filtration – to isolate Crystalline Product
VACUUM FILTRATION
- collecting crystalline solids from solvents after
recrystallization/precipitation
MELTING POINT DETERMINATION
• Melting Point – temperature at which the liquid and solid phase
exist in equilibrium with one another without change of
temperature.
• If a crystalline substance is pure, it should melt over a narrow or
sharp range, which will normally be no more than 1oC if the melting
point is determined carefully.
• Depressed Melting Point - presence of an impurity generally
decreases the melting point of a pure solid.
Video #1. Recrystallization MIT Digital Lab Techniques
• Purification of crystalline solids
5 STEPS
1. Choosing an appropriate solvent based on solubility of sample.
2. Dissolution of sample (hot)
3. Decoloration & Hot Filtration
4. Cooling
5. Collecting & Washing
Boiling Stones - added to liquids to make them boil more calmly and
prevent bumping and boiling over and loss of the solution.
ONE-SOLVENT RECRYSTALLIZATION
1. CHOOSING A SOLVENT
• Ideal solvent - Insoluble at room temperature, but soluble at
boiling point. (Winner: Ethanol)
2. DISSOLUTION OF SAMPLE
• Dissolve ethanol in a hot water bath. Do not forget to put boiling
stones.
• Place sample in an Erlenmeyer flask and set aside a pinch for
Cooling (Step 4)
• In dissolving sample, use a minimal amount of hot solvent in small
amounts w/ swirling and heating until it all dissolves.
Note: If it won’t dissolve, it’s probably an impurity or a boiling stone.
3. DECOLORIZATION & HOT FILTRATION
• Impurities can be removed through decolorization/hot filtration.
• Soluble impurity – when you expect a clear solution but you get a
yellow solution.
• Activated charcoal can absorb impurities (must be slightly below
Bp temp) small amount only!
• Swirl and Boil for 2-3 minutes.
• Charcoal is removed by filtering agent (Celite), swirl and heat again
from 2-3 minutes.
3b. Hot Filtration
- It is better to use gravity filtration (flute filter) since vacuum filtrations
cool the solution too much and crystals are lost in the filter paper and
funnel.
• Before filtering, add some excess solvent and heat to the boiling
point to ensure compounds stays dissolve during filtration.
• Wet the filter paper with hot solvent and filter the solution.
• Rinse the Erlenmeyer flask two or three times with hot solvent
filtering each rinse.
• Rinse the filter paper with hot solvent to minimize product loss.
- Crystals frequently form in the filtrate during the filtration but they easily
re-dissolve with heating.
- Remember to boil away excess solvent. Remember to add boiling
stones to the solution and boil until solid begins to form.
• Add a small amount of hot solvent to re-dissolve solid.
• Once dissolved in the minimum amount of solvent, set it aside to
cool.
• Cover to protect it from airborne particles and allow to cool at room
temperature. UNDISTURBED
- It can also be placed in a beaker stuffed with a paper towel to slow
down cooling and promote slow crystal growth.
4. COOLING
• Set aside to cool at room temperature undisturbed.
• Fun fact: Beaker w/ towel is also good to slow down cooling and
promote slow crystal growth.
• If ayaw: Scratching or add Seed Crystal or Dipping
• When crystallization has begun at room temperature, place in an
ice batch for at least 15 minutes to drive the crystallization to
completion.
5. COLLECTING & WASHING
• Flask of iced cold solvent and a vacuum filtration set up.
• Wet the filter with small amount of ice-cold solvent.
• Transfer crystals and mother liquor to vacuum.
• Use cold solvent to wash the crystals and pull the air through them
to begin drying process.
• Scrape crystals to a weighing dish and begin drying process.
• desiccator, oven or vacuum line
TWO-SOLVENT RECRYSTALLIZATION
• Attach drying tube at top and condenser at side.
• Connect water inlet and outlet tubes.
• Raise the jacket and turn on the heating source.
Experiment Steps:
• 10 g acetaminophen in a 50 mL round bottom flask
• + 10 mL ethanol and stir bar
• + 0.6-0.7 mL of 50% sodium hydroxide solution
• Stir acetaminophen until dissolved
• Heat and Stir continuously. A water bath on a hot plate is an ideal
heating source. (medyo pink dito)
• Carefully remove condenser and add 20 mmol bromoethane to
flask.
• Heat to gentle reflux to 1-1.5 hours. (medyo orange dito?)
• Once reflux is complete, remove heat source.
• Add 20 mL hot water down the condenser and briefly stir mixture.
• Crystallization is to occur within 2-3 minutes.
• Once crystallization appears, ice bath the mixture in 15 minutes.
• Vacuum filter the crystals and wash w/ cold water.
• Store until dry.
• Weigh and determine melting point range of the product.

1. CHOOSING A SOLVENT
• Solvent 1: Soluble at Room Temperature
• Solvent 2 – Insoluble even at Boiling Point

- Two solvents must be miscible to not separate in solution.

Winner: Acetone and Water

2. DISSOLUTION OF SAMPLE
• In dissolving sample, use a minimal amount of hot solvent #1 in
small amounts w/ swirling and heating until it all dissolves.
• Add just enough solvent 1 until clear solution.

3. SOLVENT MIXING
• Add solvent 2 dropwise until cloudiness persists.
• Swirl and heat the solution to make sure cloudiness persists.

Note: Do not confuse cloudiness and turbidity.

• When cloudy, add again hot solvent 1 dropwise just until solution
becomes clear.

4. COOLING/CRYSTALLIZATION

5. COLLECTING & WASHING (EQUAL RATIO)

• One recrystallization is complete, cool down a mixture of solvents
in a ratio similar to that which you recrystallized from. The cold
mixture will be used to collect and wash the crystals.

Experiment 3B – Williamson Ether Synthesis of

Phenacetin
• Synthesis phenacetin from acetaminophen

Set Up:
• Grease Round Bottom Flask then secure with clamps on a ring
stand
• Attached a condenser to a top of round bottom flask. Make sure
clamps are high enough to allow space for adjunct and a heating
mantle underneath.
o Allowable removal of heat source if needed.