Physical Chemistry Flashcards

1
Q

Define atomic number

A

The number of protons in each atom of an element

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2
Q

Define atom

A

The smallest part of an element that can take part in a chemical reaction

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3
Q

Define an element

A

A group of atoms all having the same atomic number

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4
Q

Define a molecule

A

A combination of atoms which is the smallest unit of a chemical substance that can exist whilst still retaining the properties of the original substance

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5
Q

Define atomic mass

A

The mass of one mole of an element

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6
Q

Define a mole

A

A constant number (6.022 x10^23) of atoms or molecules

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7
Q

What are isotopes

A

Elements with different numbers of neutrons but the same atomic number (same number of protons)

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8
Q

Where are the atomic and mass numbers shown in relation to the element letter

A

Atomic number subscript
Mass number superscript

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9
Q

What are the electron shells of an atom labelled

A

Innermost K the
L M N O P Q

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10
Q

Maximum capacity of the k, l m and n electron shells

A

K 2
L 8
M 18
N 32

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11
Q

What is valency

A

The number of atoms of hydrogen that one atom of an element can combine with or replace
The number of electrons an atom can loose or gain to gain stability - with by loosing in ionic bonding or sharing in convalent bonding. Depends on the electron configuration.

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12
Q

What is the valency of carbon? Why is this important

A

Valency of 4
It is very versatile, can either loose or gain 4 electrons to achieve electrical stability .

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13
Q

How does an ionic bond work

A

An atom donates an electron to another giving both stable outer shells but opposite charges resulting in attraction

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14
Q

What electron configurations confir stability

A

Full shells
Pairs
Octets

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15
Q

What is a dative bone

A

A type of covalent bond where both electrons come from the same atom
Occurs when loan pairs of electrons are in the outer shell in the unbonded state

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16
Q

What is the shape characteristics of ionic and covalent bonds

A

Ionic have no electron sharing thus bond non directional and no particular shape
Covalent have distinct shapes

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17
Q

What type of substances do ionic and covalent bonded molecules form

A

Ionic - usually solid, usually crystalline, easily dissolvable, hard to vapourise
Covalent - usually highly volatile liquid or gas, not readily soluble in water, readily vapourised

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18
Q

What are van der waals forces

A

Electrons not rigidly fixed thus attracted to charges so distribution becomes uneven producing a dipole thus undergo attraction and repulsion to similar neighbouring molecules

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19
Q

What are hydrophobic bonds, why do they form
How can it be overcome

A

Grouping of areas of uniform charge (not polar) as don’t bond to hydrogen bonds, thus energy required to split uniform bond would be greater than the energy produced by formation of new ones (as no new ones form). There is no direct attraction between the hydrophobic areas, just lack of attraction of water!
Vigerous mixing for example gives the energy to overcome the hydrogen bonds temporarily

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20
Q

What is an emulsion

A

Mixture of two or more immiscible liquids, one existing as particles within another

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21
Q

How is propofol held in emulsion

A

Propofol molecule surrounded by phospholipids in a micelle

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22
Q

Strength of main intermolecular bonds

A

Covalent - 50-150kJ/mol
Ionic - 5-10kj/mol
Hydrogen - 2-5kJ/mol
Van der waals - 0.5kJ/mol

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23
Q

What is the implication of covalent bonds in pharmacology

A

Very strong and hard to break, require catalyst or enzyme to split eg. Metabolism of entire drug:receptor complex or replacement of receptor

24
Q

What is the relationship between force of attraction of a bond and distance for ionic and van der waals

A

Ionic: force directly proportional to 1/distance^2
Vdw: force directly proportional to 1/distance^7
Very close vdw repel due to nearby electron groups

25
What are oxidation and reduction Why called oxydation?
Oxidation - loss of electrons Reduction - gain of electrons Oxydation can also be considered as gain of a proton e.g. local anaesthetic ionisation Loosing an electron means you need to give it to an electron acceptor eg forming a bond with oxygen
26
What is diffusion
The movement of molecules or ions within a gas or solution down concentration and electrical gradients until those gradients disappear resulting in an even distribution of all molecules or ions within the container
27
What is the law of gaseous diffusion? What is it?
Grahams law Rate directly proportional to 1/sqroot density At given temp and pressure
28
What is the key property of ionised vs non ionised drug and vica versa
Ionised water soluble Non ionised can cross membranes
29
What is the dissociation equation for a weak acid What is the relationship with pH
HA reversible H+ + A- pH = pKa + log 10 [A-]/[HA]
30
What is pKa
Negative log of dissociation constant The pH at which drug is 50% ionised
31
How does ionic dissociation relate to thiopental What is its pKa
pKa 7.8 Made up in an alkaline solution pH11 so ionised and soluble Enters acidic body and becomes unionised so can penetrate membranes and have effect on CNS
32
What is a partition coefficient
Numerical constant that is the ratio AT EQUILIBRIUM or the concentrations of that substance in two adjacent compartments separated by an interface through which the substance readily passes The interface can be a physical boundary such as a cell membrane or a liquid gas interface
33
What are the Ostwald partition coefficients How do they reach equilibrium
The blood gas coefficient of a gas at 37oC Gases travel down their partial pressure gradient until pp is equal in both compartments (which usually means different concentrations to obtain that equal pp)
34
By Ostwald partition coefficients what influences the concentration of a molecule for a given partial pressure in a particular compartment What about the amount of the molecule?
Affinity of the molecule for the constituents of the compartment Amount also influenced by size of the compartment
35
What is the blood gas coefficient for sevoflurane What does this mean
0.69 At equilibrium for every 1% sevoflurane in gas there will be 0.69% in the blood
36
What is osmosis
The passage of solvent through a semipermeable membrane separating two compartments having different concentrations of solutes to which the membrane is impermeable.
37
What is osmotic pressure
The pressure required to stop the movement of solvent across a semipermeable membrane
38
Differentiate osmolality and osmolarity
Osmolality is concentration by mass of solution (mOsm kg-1 H2O) Osmolarity is concentration by volume of solvent (mOsm L-1)
39
What is mannitol Why is it an effective osmotic diuretic
A high molecular weight alcohol It is filtered at the glomerulus and not reabsorbed. It has high osmotic potential so draws water after it.
40
What is an isomer
A chemical compound that has the same empirical molecular formulae but differing physical or chemical properties
41
Define a structural isomer Types
Presence of different structures with the same empirical molecular formulae Chain isomer - carbon skeleton varies between isomers with same functional groups Position isomer - component atoms or functional groups are in different positions on an identical carbon skeleton Functional group isomerism - change in functional group - eg alcohol to ether
42
What is dynamic isomerism Another name Example
Tautomerism Variant of functional group isomerism where two isomers exist in dynamic equilibrium Changes in the environment can change this equilibrium eg ph Eg thiopental and nitrous oxide
43
What is stereoisomerism Types
Same molecular formula, carbon skeleton and structure but different spatial arrangement. All molecular bonds are the same but arrangement different Optical isomerism Geometric (cis-trans) isomerism
44
What is optical isomerism Requirements
Atoms which are at least tetravalent (four bonds) with different groups of atoms on each bond Has a chiral centre (usually a carbon). If two of the groups are interchanged then it forms a non-superimposable mirror image of the original.
45
What do optical isomers produce Features
Separate enantiomers Different cysteine structures and rotate polarised light in the opposite direction.
46
How can stereoisomers be classified
Handedness (prioritising groups around chiral centre based on atomic number). can be right handed (R or D) or left handed (L or S) - note s for sinister, as in left handed people are the sinister. D is for dexter. Can also be classified by rotation of light - clockwise rotation is symboled with + or d, anti-clockwise rotation is symbolised with - or l. Note you can be either handedness with either rotation (eg D- or D+)
47
What handedness are most carbohydrates? What about proteins?
Most carbohydrates are right handed (eg D+glucose = dextrose) Most amino acids are left handed (except for glycine which has no chiral centre and some right handed amino acids in bacterial cell walls)
48
What are the potential pharmacological effects of different enantiomers
Different potencies Different side effects Naturally occurring receptors are often steriospecific cancelling out one of the enantiomers form having an effect Most drug level measurements doesn’t distinguish stereoisomers and thus needs to be accounted for in pharmacokinetic calculations Elimination may also differ between enantiomers, as can metabolite activity Redundant enantiomer (eg R bupivicaine) can still cause unwanted effects
49
What is the term for a non superimposable non mirror image sterioisomer? What are the subcategories
Diastereomer Isomers with multiple chiral centres Cis-trans isomers
50
What is a geometric isomer
Atomic orientational variation around a double bond If the main parts of each half are in the same side of the bond it’s cis (or e) , on opposite it’s trans (or z)
51
What geometric isomerisation is exhibited by mivicurium
Two double bonds with geometric isomerism so can be Cis cis Cis trans Trans trans
52
What is the difference between cis and racemic atricurium
Cis atricurium supposedly causes less histamine release
53
Which main plasma proteins are involved in drug transport
Albumin Globulin
54
Molecular weight of albumin
69,000 daltons
55
Features of albumins drug binding sites
Multiple and non specific Facility for many weak bonds (hydrogen, hydrophobic, vdw)
56
Factors that can effect drug:plasma protein binding
Amount of protein - can be influenced by surgery, trauma, mi, ca, ra Abnormalities in protein structure PH Presence of other drugs
57
In what cases are changes in protein binding of drugs producing more pronounced effects?
In highly protein bound drugs In less protein bound drugs large changes need to occur before any effect is noted.