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A-level Chemistry: 3.3.3 Halogenoalkanes

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These flashcards describe halogenoalkanes as alkanes with halogen substitutions, highlighting their physical properties such as low water solubility, intermolecular forces, and factors affecting boiling points, including chain length, halogen type, and polarity.

What is a halogenoalkane?

Alkanes with at least one halogen atom in place of hydrogen atom

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Key Terms

Term
Definition

What is a halogenoalkane?

Alkanes with at least one halogen atom in place of hydrogen atom

Describe 3 physical properties of halogenoalkanes

  • Insoluble in water ∵ polar Cδ+—Xδ- bonds are not polar enough

  • Main intermolecular forces of attraction are dipole—dipole att...

Boiling points increase with … & increases when …

Boiling points increase with increased chain length & increases when going down the halogen group

Why do boiling points increase with increased chain length or when going down the halogen group?

∵ larger the molecule = greater the number of electrons ∴ greater the van der Waals forces

Why do halogenoalkanes have higher boiling points than alkanes with similar chain lengths?

∵ have higher relative molecular masses & more polar

Why are carbon-halogen bonds polar?

Halogens are much more electronegative than carbon

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TermDefinition

What is a halogenoalkane?

Alkanes with at least one halogen atom in place of hydrogen atom

Describe 3 physical properties of halogenoalkanes

  • Insoluble in water ∵ polar Cδ+—Xδ- bonds are not polar enough

  • Main intermolecular forces of attraction are dipole—dipole attraction and van der Waals forces

  • Halogenoalkanes mix with hydrocarbons

Boiling points increase with … & increases when …

Boiling points increase with increased chain length & increases when going down the halogen group

Why do boiling points increase with increased chain length or when going down the halogen group?

∵ larger the molecule = greater the number of electrons ∴ greater the van der Waals forces

Why do halogenoalkanes have higher boiling points than alkanes with similar chain lengths?

∵ have higher relative molecular masses & more polar

Why are carbon-halogen bonds polar?

Halogens are much more electronegative than carbon

What makes halogenoalkanes prone to attacks from nucleophiles?

δ+ charge on carbon/polar carbon-halogen bond

What is a nucleophile?

Electron-pair donor

(negatively charged ion or an atom with δ- charge)

What do nucleophiles have?

Has lone (unshared) pair of electrons

As you go down the halogen group, the bonds (C-X) get __ ___

less polar

What is a nucleophilic substitution reaction?

When a nucleophile reacts with polar molecules by replacing the functional group

Why are nucleophilic substitution reactions used?

To introduce new functional groups into organic compounds

Nucleophilic Substitution

Name the reactant

Halogenoalkane

Nucleophilic Substitution

Name the nucleophiles

:OH-, :CN- & :NH3

Nucleophilic Substitution

Name the condition & product for the nucleophile :OH-

Warm, aqueous NaOH or KOH → Alcohol

Nucleophilic Substitution

Name the condition & product for the nucleophile :CN-

Warm halogenoalkane with ethanolic KCN(aq) → Nitrile

Nucleophilic Substitution

Name the condition & product for the nucleophile :NH3

Warm halogenoalkane with excess ethanolic ammonia → Amine

Why is the reaction between hydroxide ions & halogenoalkanes sometimes called hydrolysis?

∵ in the mechanism, the exact same reaction will happen with water

Bromoethane + aqueous NaOH

Name the mechanism

Nucleophilic Substitution

Bromoethane + aqueous NaOH

Balanced Equation

C2H5Br + NaOH → C2H5OH + NaBr

Bromoethane + aqueous NaOH

Name of Organic Product

Ethanol


Bromoethane + aqueous NaOH

Mechanism

Bromoethane + NH3

Name of Mechanism

Nucleophilic Substitution

Bromoethane + NH3

Balanced Equation

Bromoethane + NH3

Mechanism

Bromoethane + NH3

Name of Organic Compound

Ethylamine

Bromoethane + KCN

Name of Mechanism

Nucleophilic Substitution

Bromoethane + KCN

Mechanism

Bromoethane + KCN

Balanced Equation

C2H5Br + KCN → C2H5CN + KBr

Bromoethane + KCN

Name of Organic Compound

Propanenitrile

When halogenoalkanes react with ammonia, what can the amine group in the product act as and why & what can this lead to?

Can acts as nucleophile∵ it has lone pair of electrons ∴ may react with halogenoalkane molecules = giving mixture of products

Why is an excess of ammonia needed to react with a halogenoalkane to produce a high yield?

  1. The amine group in the product = nucleophile ∴ could react further & make secondary/tertiary amines OR

  2. Ammonia acts both initially as a nucleophile and then as a base

What 2 factors affect the carbon-halogen bond's reactivity?

  • Cδ+—Xδ- bond polarity

  • C—X bond enthalpy (i.e. strength)

Bond Enthalpies

Bonds get ____ going down the group

Bonds get weaker going down the group

Explain why fluorine has the strongest bond

It's the smallest atom of halogens & shared electrons in C—F bond = strongly attracted to nucleus

Explain why bonds get weaker going down the group

∵ shared electrons in C—X bond gets further away from halogen nucleus = bond becomes weaker

What does the polarity of C—X predict & why?

  • C—F most reactive

    • ∵ its most polar - Cδ+ has most positive charge ∴ more easily attacked by nucleophile

  • C—I = least reactive

    • ∵ it's least polar

What is the main factor that decides reactivity?

Carbon-halogen bond enthalpy

(Experiments show that reactivity increases down the group ∵ bond enthalpy is more important factor than bond polarity)

Why do fluoroalkanes undergo nucleophilic substitution reactions more slowly than other halogenoalkanes?

C-F bond is strongest = highest bond enthalpy

Why are iodoalkanes substituted more quickly than say fluoroalkanes?

C-I bond has lowest bond enthalpy = easier to break

When do you get an elimination reaction?

If you warm a halogenoalkane with hydroxide ions dissolved in ethanol instead of water = elimination reactions happens

Elimination Reaction

Name the condition and product when a halogenoalkane is used as a rectant

Ethanolic KOH - Alkene

2-bromopropane + ethanolic KOH

Name of Mechanism

Elimination Reaction

2-bromopropane + ethanolic KOH

Balanced Equation

C3H7Br + KOH → C3H6 + H2O + KBr

2-bromopropane + ethanolic KOH

Name of Organic Compound

Propene

In an elimination reaction, why do you have to heat mixture under reflux?

∵ you'll otherwise lose the volatile stuff

In elimination reactions: small group of atoms….

break away from molecule

Group is NOT replaced

When halogenoalkanes are reacted with hydroxides, they can undergo…

either nucleophilic substitution or elimination → 2 reactions are said to be competing

Identify & draw an isomer of 2-bromopentane that does not react with hot, ethanolic sodium hydroxide to produce an alkene

1-bromo-2,2-dimethylpropane

Suggest one change to the reaction conditions that would increase the yield of an alcohol

(Hot concentrated ethanolic potassium hydroxide reacts with halogenoalkane)

  • Use water as a solvent (aq conditions)

  • Lower temperature

  • Dilute KOH

Suggest one change to the reaction conditions that would increase the yield of an alkene

  • Ethanolic solvent

  • High temperature

  • High concentration of KOH