PART 3

SCIENTIFIC
CALCULATIONS
In addition to teaching the specialist skills of the pharmacist, the
pharmacy degree is also respected as a good broad-based scienti ic
degree. This section of the workbook aims to help you to apply basic
mathematics to solve scienti ic problems that you will commonly
encounter throughout the pharmacy degree.

1. REARRANGING FORMULAE
T o solve a scienti c problem, it is often necessary to rearrange formulae. We have already seen examples of
such rearrangements in this workbook, for example the general formula C1V1 = C2V2 has been rearranged in
C1V1
order to calculate the concentration of a diluted solution: C2 = .
V2

GENERAL RULE
We may always alter both sides of an equation in the same way without changing the truth
of the statement.

This manipulation may be an addition or subtraction, multiplication, division, logarithm, power or

root ... any mathematical manipulation we choose provided the same operation is performed to
both sides of the equation.

EXAMPLE
For example, given the following equation of a straight line, we may be asked to calculate the
value of x:
y = mx + c
Putting of the left hand side:
mx = y − c
… and then divide both sides by :
(y − c)
x=
m
Which is a very simple rearrangement, of course: But, you will note that in the last stage we had
to divide all the elements of the equation by m.

47
fi
f
f
Let's try some more:

EXAMPLE
From the following identify the value of x:
y = 5x 2 − 17

The same process applies, so we start by getting just x on the left:

5x 2 − 17 = y
5x 2 = y + 17
y + 17
x2 =
5
… and nally take the square root of both sides to identify x:
y + 17
x2 =
5

EXAMPLE
From the following identify the value of x:
3
y= x −1

3 1
Rearranging and writing x as x 3 :
1
x3 − 1 = y
1
x3 = y + 1

… and nally we raise both sides to the power of 3 to identify x:

x = (y + 1)
3

… and often we will even be able to work out the answer:

EXAMPLE
Given the following, calculate the value of x:
x + 73 = 132

x = 132 − 73
∴ x = 59

48
fi
fi
3 Scientific Calculations 53
3 Scientific Calculations 53
Indicate the correct answer.
Test yourself
3 Scientific Calculations Given thethe
following, what is the value of x? 53
Indicate correct answer.
Test yourself Q60 Given thethe
following, whaty = x2 +
is the value
57 of x?
Indicate correct answer.
Test yourself Q60 Given the following, what y = x2 +
is the value
57 of x?
Q60 A x = y − 57 y = x + 57 2

B
A xx =
= y y− − 5757
C
B
A xx =
= y y− −+ 57
57
x = (yy ++ 57)
D 2
C
B − 57
E
D
C xx =
= (yyy +− 57)
57
+ 57
2
Answer
E
D xx =
= (yy +− 5757)2
A
Answer x = y − 57
E B C D E
O
A
Answer O
B O
C O
D O
E
O O
B answer. O
A the correct
Indicate C O
D O
E
Test yourself GivenOthethe O answer.
following, what isO
the value ofOx? O
Indicate correct
Test yourself
Q61 Given thethefollowing, whaty is=the + 57 of x?
x value
Indicate correct answer.
Test yourself
Q61 Given the following, whaty is=the + 57 of x?
x value
Q61 A x = y − 57 y = x + 57
B
A xx == y y− − 5757
C
B
A xx == y y− −+ 57
57
x = (yy ++ 57)
D 2
C
B − 57
E
D
C xx =
= (yyy +− 57)
57
+ 57
2
Answer
E
D xx =
= (yy +− 5757)2
A x = yB− 57
Answer
E C D E
O
A
Answer O
B OC O
D O
E
O O
B answer. O
A the correct
Indicate C O
D O
E
Test yourself GivenOthethe O answer.
following, what isO
the value ofOx? O
Indicate correct
Test yourself
Q62 Given thethefollowing, 2
what
5x + is8 the
= value
x2 + 57
of x?
Indicate correct answer.
Test yourself
Q62 Given the following,5x 2
what+ is8 the
= value
x2 + 57
of x?
Q62 A x = 3·5 5x + 8 = x + 57
2 2

B
A xx =
= 37·0
3·5
xx =
x =
C 49 4
B
A = 37·0
3·5
C
D
B xx = 4
49
= 37·0
49 4
E
C
D x = 1 44949 4
Answer
E
D x = 14 49
A
Answer B C D E
E x = 1
O
A
Answer O
B O
C O
D O
E
O
A O
B O
C O
D O
E
O
PHAR1001 Mathematics O
Tutorial O
Workbook O 2014
April O
PHAR1001 Mathematics Tutorial Workbook April 2014
PHAR1001 Mathematics Tutorial Workbook April 2014

49
The last question actually looks more frightening than it is. Here's how I would tackle it:

5x 2 + 8 = x 2 + 57

5x 2 − x 2 = 57 − 8
4x 2 = 49
49
x2 =
4
49
∴x=
4
49
=
4
7
= ± = ± 3.5
2

… where we remember that square roots can be either positive or negative in the sense that, for example:
−2 × −2 = 2 × 2 = 4.

Commonly, you will also come up against the situation where one number is equal to another raised to a power of
x. For example we might consider the case of:
y = A × e −k× x
In such cases, where you encounter e raised to some power, the trick is to take the natural logarithm (the
logarithm to the base of e) of both sides of the equation:
ln (y) = ln (A × e −k× x)
= ln (A) + ln (e −k× x)
= ln (A) + (−k × x)
= ln (A) − k x

This is an especially useful manipulation that you will encounter time and time again.

Sometimes, you will also encounter the general scienti c puzzle of a curved graph where y ∝ x n, where the power
of x, (n) is unknown. Here too, logarithms are most useful.

GENERAL RULE
Given the general case of:

y = a × xn
lg (y) = lg (a) + n lg (x)

From which it follows that plotting lg (y) against lg (x) yields a straight line of y-intercept lg (a)
and a gradient of n.

50
fi
whence it follows that plotting lg (y) against lg (x) yields a straight line of y-intercept lg (a) and
gradient of n.

Indicate the correct answer.

Test yourself Given the following, what is the value of the y-intercept after
Q63 plotting lg (y) against lg (x)?
y = 100 × x5

A x = 100
B x = 3
C x = 2
D x = 5
E x = lg (5)

Answer
A B C D E
O O O O O

OK that
OK that looks
lookshard
hard…...but
butagain
againit is
it just thethe
is just sumsum
of the
of simple elements
the simple you already
elements know. Let's
you already know.doLet's
it together:
do it together:
y = 100 5 x5
y = 100 × x×
lg (y) (= )lg (100) + 5 lg (x)
∴ lg y = lg (100) + 5 lg (x)
∴
remembering that 100 = 10 2
:
remembering that 100 = 10 2:
lg (y) = lg (102) + 5 lg (x)
lg (y) = lg2(y+) 5= lg
lg((x10
) ) + 5 lg (x)
2

… so plotting Y = lg (y) against X = lg (x) yields a straight line of gradient 5 and y-intercept 2:
... and plotting Y = lg (y) against X = lg (x) then yields a straight line of gradient 5 and y-
intercept 2.
Y = 2 + 5X
Y = 2 + 5X
56 3 Scientific Calculations
PHAR1001 Mathematics Tutorial Workbook April 2014
Indicate the correct answer.
Test yourself Given the following, what is the value of the y-intercept after
Q64 plotting lg (y) against lg (x)?
y = 1000 × x5
A x = 1000
B x = 10
C x = 4
D x = 5
E x = 3
Answer
A B C D E
O O O O O
Indicate the correct answer.
Test yourself Given the following, what is the gradient of the line obtained
Q65 by plotting lg (y) against lg (x)?
y = 1000 × x5
A x = 1000 51
B x = 10
C x = 4
 E
D xx =
= 35
Answer
E x = 3
A
Answer B C D E
O
A O
B O
C O
D O
E
O the correct
Indicate O answer. O O O
Test yourself Given thethe
following, what is the gradient of the line obtained
Indicate correct answer.
Test yourself
Q65 Given the following, whatlgis(xthe
by plotting lg ( y) against )? gradient of the line obtained
Q65 by plotting lg (y) against
y = (x)? × x5
lg 1000
A x = 1000 y = 1000 × x5
B
A xx =
= 10
1000
C
B x =
x = 104
D
C = 45
xx =
E
D xx =
= 35
Answer
E x = 3
A
Answer B C D E
O
A OB O
C O
D O
E
O the correct
Indicate O answer. O O O
Test yourself Given thethe
following, what is the gradient of the line obtained
Indicate correct answer.
Test yourself
Q66 Given the following, whatlgis(xthe
by plotting lg ( y) against )? gradient of the line obtained
Q66 by plotting lg (y) against (x)? × x3
y =lg57·562
A x = lg (57·562y =) 57·562 × x3
B
A xx = lg (57·562)
= 10
C
B x =
x = 10
4
D
C = 45
xx =
E
D xx =
= 35
E x = 3
Answer
A
Answer B C D E
O
A O
B O
C O
D O
E
3 Scientific Calculations O O O O O 57
PHAR1001 Mathematics Tutorial Workbook April 2014
Indicate the correct answer.
Test yourselfPHAR1001 Mathematics Tutorialwhat
Given the following, Workbook
is the value April
of x? 2014
Q67 3x3 + 3 = x3 + 57

A x = ±3·5
B x = ±3
C x = 3
D x = 227
E x = −3
Answer
A B C D E
O O O O O

Indicate the correct answer.

Test yourself Given the following, what is the value of x?
Q68 2x2 + 8 = x2 + 9

A x = ±1 52
B x = 7
9 8
C x = 2
 A B C D E
O O O O O

Indicate the correct answer.

Test yourself Given the following, what is the value of x?
Q68 2x2 + 8 = x2 + 9

A x = ±1
B x = 7
9 8
C x = 2
9
D x = 8
E x = 1·5
Answer
A B C D E
O O O O O

In these simple
In these simpleexamples,
examples,the the answer
answer is simple
is simple because
because there is there is only
only one powerone
of x power of x to beHowever,
to be considered.
considered. However, you will not encounter this in all circumstances. Commonly,
you will not encounter this in all circumstances. Commonly, you will need to work out the solution youto will
problems
need to
such as: work out the solution to problems such as:

Given the following, calculate the value of x.

EXAMPLE
x2 + x = 0
Given the following, calculate the value of x:
... which cannot be solved in the simple way we have2used so far. The trick here is to rearrange
x +x =0
the equation to be something = 0, and then to say that one of the factors of the LHS must
therefore be equal to zero.
… which Taking
cannot the current
be solved example:
in the simple way we have used so far. The trick here is to rearrange
the equation to be <something> = 0, and then to say that one of the factors of the left hand side
must therefore be equal to zero. Continuing the current example:
x2 + x = 0
∴ x (x + 1) =Mathematics
PHAR1001 0 Tutorial Workbook April 2014

Since the product of x × (x + 1) = 0 it follows that one of these components must also be zero:
∴ either: x = 0 or: (x + 1) = 0
⟹ x = 0 or: x = − 1

From this argument, it follows that x 2 = n is merely a special case of exactly the same process.

EXAMPLE
Given the following, calculate the value of x:
x2 = 9

⟹ x2 − 9 = 0
(x + 3) (x − 3) = 0
∴ either: x + 3 = 0 or: x − 3 = 0
∴ x = − 3 or: x = + 3
⟹ x=±3

53
Taking a slightly more complicated example, the process of factorisation remains exactly the same:

EXAMPLE
Given the following, calculate the value of x:
x2 + x = 6

⟹ x2 + x − 6 = 0
(x + 3) (x − 2) = 0
∴ either: x + 3 = 0 or: x − 2 = 0
∴ x = − 3 or: x = + 2

3 Scientific
Try Calculations
some yourself: 59
3 Scientific Calculations 59
Indicate the correct answer.
Test yourself Given thethe
following, what is the value of x?
Indicate correct answer.
Test yourself
Q69 x2 is−the
Given the following, what = 2 of x?
x value
Q69 x2 − x = 2
A x = −2
B
A xx =
= 1−2
C
B xx =
= +2
1 or −1
D
C xx =
= −2 or
+2 +1
or −1
E
D xx =
= ±1·5
−2 or +1
Answer
E x = ±1·5
A
Answer B C D E
O
A O
B O
C O
D O
E
O the correct
Indicate O answer. O O O
Test yourself Given thethe
following, what is the value of x?
Indicate correct answer.
Test yourself
Q70 x2 +is the
Given the following, what = −6 of x?
5x value
Q70 x2 + 5x = −6
A x = +6 or −1
B
A xx =
= +2 or
+6 +3
or −1
C
B xx =
= −2 or −3
+2 or +3
D
C xx =
= +3 −3
−2 or −3
or
E
D xx =
= +1
+3 or −6
or −3
Answer
E x = +1 or −6
A
Answer B C D E
O
A O
B O
C O
D O
E
O the correct
Indicate O answer. O O O
Test yourself Given thethe
following, what is the value of x?
Indicate correct answer.
Test yourself
Q71 x2 is+ the
Given the following, what = 6 of x?
5x value
Q71 x2 + 5x = 6
A x = +6 or −1
B
A xx =
= +2 or
+6 +3
or −1
C
B xx =
= −2
+2 or −3
or +3
= +3 54
−3
D
C xx = −2 or −3
or
E
D xx =
= +1
+3 or −6
or −3
E x = +1 or −6
 Answer
A B C D E
O O O O O
Indicate the correct answer.
Test yourself Given the following, what is the value of x?
Q71 x2 + 5x = 6

A x = +6 or −1
B x = +2 or +3
C x = −2 or −3
D x = +3 or −3
E x = +1 or −6

Answer
A B C D E
O O O O O

PHAR1001 Mathematics Tutorial Workbook April 2014

2. MOLECULAR MASS
O ften we are faced with concentrations and amounts which require a knowledge of the molecular weight, also
known as the (relative) molecular mass, of a compound. The molecular mass of a compound is de ned as the
mass of one mole of that compound; where one mole is 6.02252 × 10 23 (Avogadro’s number of) molecules1.

GENERAL RULE
The relative molecular mass (RMM) of a compound is the sum of the relative atomic mass (RAM)
of the component atoms.

Thus, in the case of sodium chloride, the molecular mass of may be calculated from the molecular formula
(1 Na + 1 Cl ), as follows:
+ −

RMM (compound) = sum of component parts

RMM (NaCl) = 1 × RAM (Na) + 1 × RMM (Cl)
= (23.0 + 35.5) g mol−1
= 58.5 g mol−1

It follows that n moles of NaCl will weigh:

mass NaCL = number of moles × RMM

= n mol × 58.5 g mol−1
= (58.5 × n) g

1You will recall that one mole of gas under s.t.p. (standard temperature and pressure) conditions occupies a
volume of 1 dm3 = 1 L, which is the origin of Avogadro’s number.
55
fi
… and likewise we may calculate the number of moles:

EXAMPLE
How many moles of NaCl are present in 1·0 kg
1 kg 1000 g
Quantity NaCl = ×
58.5 g mol−1 kg
= 17.09401709... mol
= 17 mol (2 sf)

3 Scientific Calculations 61

Indicate the correct answer.

Test yourself
3 Scientific Calculations
What is the molecular mass of Sodium Sulphate (Na2 SO4)?
61

Test yourself Q72 (RMM

IndicateNa=23·0, S=32·1,
the correct O=16·0)
answer.
What is the molecular mass of Sodium Sulphate (Na2 SO4)?
−1
Q72 A
(RMM 110·1 g mol
Na=23·0, S=32·1,
−1
O=16·0)
B 136·1 g mol
C
A 142·1 g mol −1
110·1
D
B 136·1 g mol −1
126·1
E
C 116·1 g mol −1
142·1
Answer 126·1 g mol −1
D
E A 116·1 g B mol −1 C D E
O
Answer O O O O
A B C D E
O the correct
Indicate O answer. O O O
Test yourself How many moles of Hydrocortisone Butyrate (RMM=432·6)
Q73
Test yourself
are present
Indicate theincorrect
100 g?answer.
How many moles of Hydrocortisone Butyrate (RMM=432·6)
Q73 A present
are 0·23
in mol
100 g?
B 0·46 mol
C
A 2·3
0·23mol
mol
D
B 4333000
0·46 mol mol
E
C 43·3mol
2·3 mol
Answer
D 4333000 mol
E A 43·3 molB C D E
O
Answer O O O O
A B C D E
O the correct
Indicate O answer. O O O
Test yourself How many moles of fluoride are contained in 100g of
Q74
Test yourself
Sodium
Indicate Fluoride?
the correct(RMM NaF=41·9, RAM Na=23·0)
answer.
How many moles of fluoride are contained in 100g of
Q74 A 0·24 mol (RMM NaF=41·9, RAM Na=23·0)
Sodium Fluoride?
B 2·39 mol
C
A 4·34
0·24 mol
mol
D
B 43·3 mol
2·39 mol
E
C 54·9 mol 56
4·34
Answer
D 43·3 mol
E A 54·9 molB C D E
O O O O O
 A B C D E
O O O O O

Indicate the correct answer.

Test yourself How many moles of fluoride are contained in 100g of
Q74 Sodium Fluoride? (RMM NaF=41·9, RAM Na=23·0)

A 0·24 mol
B 2·39 mol
C 4·34 mol
D 43·3 mol
E 54·9 mol
Answer
62 3 Scientific Calculations
A B C D E
O O O O O
Indicate the correct answer.
Test yourself What mass of sodium is contained in 100 g of Sodium
Q75 PHAR1001 Mathematics Tutorial
Fluoride? (RMM Workbook
NaF=41·9, RAM Na=23·0)
April 2014

A 0·24 g
B 2·39 g
C 4·34 g
D 43·3 g
E 54·9 g
Answer
A B C D E
O O O O O

Perhaps the last two examples seem a little hard to do in your

Hint
HINT head. Again this is merely exercising the skill of
approximation.
Perhaps the last two examples seem a little hard to do in your head—this is exercising the skill of
approximation

How many moles of fluoride are contained in 100g of Sodium Fluoride? (RMM NaF=41·9,
RAM Na=23·0).
EXAMPLE
Noting that there are 1 atoms of Fluorine present in 1 molecule of NaF ...
How many moles of uoride are contained in 100g of Sodium Fluoride? (RMM NaF=41·9, RAM
−1
No. moles f luoride = No. moles NaF = 100g ÷ 41·9 g mol
Na=23·0).

(100 of÷ NaF

We note that there are 1 moles of F present in≈1 moles 40) mol
…

moles of≈F
=2·5moles
mol of NaF = 100 g ÷ 41.9 g mol−1
100
≈
What mass of sodium is contained in 100 g of Sodium Fluoride? mol
40(RMM NaF=41·9, Na=23·0)
≈ 2.5 mol
Noting that there are 1 atoms of Sodium present in 1 molecule of NaF ...
HINT
No. moles Sodium = No. moles NaF = 100g ÷ 41·9 g mol
−1

There are two lessons to learn in the above example:

(100quoting
≈ when
1. Chemists frequently omit to state the units ÷ 40) mol
RAM or RMM values.
2. You may not need all the information given to you in a question —here we did not need to
know the RAM of sodium.
≈ 2·5 mol
−1
∴ mass Sodium ≈ 2·5 mol × 23 g mol
57
≈ 57·5 g
fl
 EXAMPLE
What mass of sodium are contained in 100g of Sodium Fluoride? (RMM NaF=41·9, RAM
Na=23·0).

We note that there are 1 moles of Na present in 1 moles of NaF …

moles of Na = moles of NaF = 100 g ÷ 41.9 g mol−1

100
≈ mol
40
≈ 2.5 mol
∴ mass of Na ≈ 2.5 mol × 23g mol−1
≈ 57.5 g

HINT
The last two questions are paired — if the rst is answered correctly the second becomes trivial.

HINT
There is another way of tackling the last question that does not require you to calculate
3 Scientific Calculations 63the
number of moles of Na present — the secret is to do the question by relative amounts:
Note that the last two questions are actually paired ... such that if the first is answered correctly
23 g mol−1
the second is almost trivial! mass Na = × 100 g
41.9 g mol−1
1
Another way of tackling the last question is by relative amounts:
≈ × 100 g [well a bit over that]
23 g mol −1 2
mass Sodium = × ≈ 50gg
100
41·9 g mol −1
… close enough! 1
≈× 100 g (well, just over)
2
... which would have been close enough in this case.

Indicate the correct answer.

Test yourself What mass of fluorine is contained in 100 g of Sodium
Q76 Fluoride? (RMM NaF=41·9, RAM F=19·0)

A 0·24 g
B 2·39 g
C 4·53 g
D 45·3 g
E 54·9 g

Answer
A B C D E
O O O O O

3.4 Molar solutions

58
In chemistry, it is usually more relevant to express the concentration of a solution in terms of the
number of molecules present, rather than the mass of chemical present. Clearly, this is the most
obvious form to employ when one (or more) chemicals is being reacted with another.
fi
3. MOLAR SOLUTIONS
In chemistry, it is usually more relevant to express the concentration of a solution in terms of the number of
molecules present, rather than the mass of chemical present. Clearly, this is the most obvious form to employ
when one (or more) chemicals is being reacted with another.

A molar solution (1 M) is de ned as containing 1 mole of molecules per 1 L ( = 1 dm3 or 1000 mL) of liquid.

Thus we will frequently come across situations when we will have to translate between mass of chemical (or drug)
and the number of molecules present in solution.

EXAMPLE
The result of a titration is that a solution contains 0.2 M Aspirin; how much drug is present in
64 100 mL? (RMM Aspirin=180) 3 Scientific Calculations

Quantity = Concentration × Volume

You will recall that: = 0.2 M × 100 mL
Quantity = Concentration × Volume 0.2mol 180 g
= × 100 mL ×
1000 mL mol
= 0·2 M × 100 mL
0.2mol 180 g
0·2 mol = 180 g × 100 mL ×
= × 100 mL ×1000 mL mol
1000 mL = 0.2 × 18 g
mol
⁄ o⁄ ⁄l 180⁄ g
⁄ L⁄= ×3.6 g
0·2 m
= × 10⁄ 0⁄ m
10⁄ 0⁄ 0⁄ m⁄ L⁄ m⁄ o⁄ ⁄l
NO CALCULATOR
= 0·2NEEDED
× 18 g
Again, most of the mathematics cancels out to leave a trivial sum to do.
= 3·6 g
... and again most of the mathematics cancels out leaving a trivial sum to do.

Indicate the correct answer.

Test yourself What mass of Aspirin (RMM =180) is required to
Q77 manufacture 200 mL of 0·5 M solution?

A 9·0 g
B 12·0 g
C 18·0 g
D 27·0 g
E 36·0 g
Answer
A B C D E
O O O O O

Indicate the correct answer.

Test yourself What mass of Penicillamine (RMM =149·2) is required to
Q78 manufacture 100 mL of 0·5 M solution?

A 14·9 g
B 149 g
C 74·6 g
D 7·46 g 59
E 3·60 g
Answer
A B C D E
fi
 A B C D E
O O O O O

Indicate the correct answer.

Test yourself What mass of Penicillamine (RMM =149·2) is required to
Q78 manufacture 100 mL of 0·5 M solution?

A 14·9 g
B 149 g
C 74·6 g
D 7·46 g
E 3·60 g
Answer
3 Scientific Calculations A B C D E 65
O O O O O

Indicate the correct answer.

Test yourself
PHAR1001 Mathematics Tutorial Workbook April 2014
Cimetidine (RMM=252·3) oral solution contains 200 mg of
Q79 drug per 5 mL, what is the molarity of this solution?
A 0·16 M
B 1·6 M
C 16 M
D 0·8 M
E 0·08 M

Answer
A B C D E
O O O O O

HINT
As usual,
As usual, the question that question
looks looks more
more difficult than complicated
it is ... than it is. Let’s do it together:

200 mg 1000 mL 1g 1 mol

200 mgmolarity
1000 1 g=
(concentration)
mL ×
1 mol × ×
Molarity = × × 5×mL L 1000 mg 252.3 g
5 mL L 1000 mg 252·3 g
40
= mol L−1 M
converting volume to Litres ↑ 252.3
converting mass to grammes ↑ ≈ 40 M
250
converting quantity to moles ↑
16
40 ≈ M
= mol L −1 100
252·3 ≈ 0.16 M
4 × 1000
≈ M (dividing 1000 by 250 is easy)
250 × 100
NO CALCULATOR 16 NEEDED
≈
Again, the value of
M
approximation is clear.
100
≈ 0·16 M

60
66 3 Scientific Calculations

Indicate the correct answer.

Test yourself Baclofen (RMM=213·7) oral solution contains 5 mg of drug
Q80 per 5 mL, what is the molarity of this solution?

A 46 M
B 4·6 M
C 0·46 M
D 0·046 M
E 0·0046 M

Answer
A B C D E
O O O O O

4. FIRST ORDER AND ZERO ORDER KINETICS

In all elements of our work as pharmacists, chemical reactions are of fundamental importance. For example, a
stored drug may undergo oxidation or hydrolysis in storage reducing the quantity of the native drug present, or,
worse still, making a toxic compound. Thus it is important that we understand not only the nature of the
degradation process, but also the rate at which it occurs.

THINK LIKE A PROFESSIONAL

In all aspects of the scienti c study you will encounter as an undergraduate, and in the wider
application of your skills as a pharmacist, two types of kinetic pro le (be it for a chemical
reaction, or absorption through the skin or release or drug from a tablet or the elimination of drug
from the body) are prevalent. These are rst-order and zero-order processes.

PHAR1001 Mathematics Tutorial Workbook April 2014

61
fi
fi
fi
 understand not only the nature of the degradation process, but also the rate at which it occurs.

In all aspects of the scientific study you will encounter as an undergraduate, and in the wider
application of your skills as a pharmacist, two types of kinetic profile (be it for a chemical
reaction, or absorption through the skin) are prevalent. These are first-order and zero-order
processes.

3.5.1 First oder kinetics

4.1.FIRST-ORDER KINETICS
F
First
irst order
order kinetics
kinetics are encountered
are encountered where
where the the concentration
concentration oftype
of a single a single type ofis molecule
of molecule is the
the rate-limiting
rate-limiting
feature feature
of a process. of a process.
Plotting the declinePlotting the decline
in concentration in molecule
of this concentration
againstoftime
thisyields
molecule against
the characteristic
exponential decaythe
time yields procharacteristic
le: exponential decay profile:

Concentration of drug vs. time

100

80
Drug Concentration / %

60

40

20

0
0 5 10
T

Figure 3.1 First order decay kinetics

Figure 3.1 First order rate kinetics
PHAR1001 Mathematics Tutorial Workbook April 2014

( )
change in drug concentration
… where the rate of the reaction at any point is the gradient of the graph = is
time
proportional to the concentration of drug remaining.

Thus, when a lot of drug (say 80 %) is present, the gradient of the line (rate of the reaction) is steep; and when
most of the drug has gone (say 10 % remaining), the reaction proceeds very slowly ...

WHY IS THIS FIRST-ORDER?

Mathematically we would write:

dy
− ∝ y1
dx
rate of reaction ↑ ↑ the concentration of reactant remaining

Thus the reaction proceeds at a rate proportional to the concentration of reactant to the power
of 1 ... hence rst order.
62
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fi
 GENERAL RULE
The equation:

dy
− ∝ y1
dx

… can be solved by integration (don’t worry, you don’t need to know how) and can always be
written in the form:

↓ the rst order rate constant (k)

Ct = C0 × e −k×t
the concentration remaining at time t ↑ ↑ time (t)
the initial concentration ↑

This is a fundamentally important which you must learn ... and you must also learn to recognise
processes which conform to this form of exponential decay.

Taking the natural (base e) logarithms of both sides of the equation:

Ct = C0 × e −kt
∴ ln (Ct) = ln (C0) − k t

This is interesting because it shows that plotting the graph of Y = ln (Ct)) against X = t will
yield a straight line of the form Y = m X + c; where the gradient m = − k is (minus) the rst-
order rate constant and the y-intercept is the (natural log of the) starting concentration of reactant
ln (C0).

GENERAL RULE
The half-life is xed and does not depend on the starting concentration (C0)

One characteristic of this type of graph, is that it takes a xed amount of time for the
concentration of reactant remaining to be halved. This amount of time is known as the half-life of

( 2)
the process written t 1 – If the starting concentration of drug is 100 % , then after one half-life

50 % remains; after two half-lives, 25 % (50 % of 50 % ) remains; and after three half-lives
12.5 % (50 % of 50 % of 50 % )remains ... and so on.

63
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fi
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fi
GENERAL RULE

( 12 )
The half-life t is related to the rst order rate constant (k).

( 12 )
At the half-life t , the concentration of drug remaining is half the starting concentration:

C0
Ct =
2

It follows that, at: time = t 1:

2

(2)
C0
ln = ln (C0) − k . t 1
2

(2)
C0
k . t 1 = ln (C0) − ln
2

( 2)
C
= ln C0 ÷ 0

( C0 )
2
= ln C0 ×

= ln (2)
ln (2)
∴ t1 =
2 k
ln (2)
and k =
t1
2

These are important deductions and should be memorised. Likewise, the value of ln (2)
( = 0.6931) is important, and is worth remembering ... although memorisation this number is
not required for the purposes of this Workbook.

64
fi
70 3 Scientific Calculations
70 3 Scientific Calculations
Indicate the correct answer.
Test yourself
70
Indicate the correctfirst-order
3 Scientific Calculations
answer. hydrolysis in aqueous solution,
Test yourself Drug X undergoes
Q81
Test yourself
Drug
with aXhalf-life
Indicate undergoes
the correctof 2first-order
hours. How
answer. hydrolysis
much drugin aqueous
remainssolution,
after 6
Q81 with
hours
Drug Xa half-life
under of 2 hours.
these conditions?
undergoes How much drug remains
first-order hydrolysis in aqueous solution, after 6
hours
with aunder theseofconditions?
Q81 half-life 2 hours. How much drug remains after 6
Ahours under
90 % these conditions?
BA 8090 %%
CB
A 80
5090 %%
%
DC
B 50
25
80 % %
%
ED
C 25
50 %
12·5 %%
E
D
Answer 12·5
25 %%
Answer
E A 12·5 % B C D E
AnswerA
O OB C
O D
O E
O
O
A O
B O
C O
D O
E
Indicate the correct answer.
Test yourself O the correct
Indicate O answer. O O O
Test yourself Drug Y is removed from the body by a first-order process. If
Q82
Test yourself
Drug
50 % Yremains
Indicate istheremoved
after from
correct 1·37 the
answer. bodywhat
hours, by a is
first-order process.
the half-life of theIf
Q82 50 %
process? remains after 1·37 hours, what is the
Drug Y is removed from the body by a first-order process. Ifhalf-life of the
process?
Q82 50 % remains after 1·37 hours, what is the half-life of the
Aprocess?46 min
BA 46 min
1·37 hrs
CB
A 1·37
2·0 hrs
hrs
46 min
DC
B 2·0
4·0
1·37hrshrs
hrs
ED
C 4·0
2·0
6·0 hrshrs
hrs
E
D
Answer 6·0 hrs
4·0 hrs
Answer
E A 6·0 hrs B C D E
AnswerA
O OB C
O D
O E
O
O
A O
B O
C O
D O
E
Indicate the correct answer.
Test yourself O the correct
Indicate O
is removed answer.
O O O
Test yourself Digoxin from the human circulation with a half-
Q83
Test yourself
Digoxin
life is removed
of about
Indicate the from much
2 days. answer.
correct How the human
remainscirculation with
in of a 250 mcga dose
half-
Q83 life of about
administered
Digoxin is removed2 days. How
by IV injection much
from theafterremains
human 4 days? in of a 250 mcg
circulation with a half-dose
administered
life of about 2by IV injection afterremains
4 days?in of a 250 mcg dose
Q83 days. How much
Aadministered
0 mcgby IV injection after 4 days?
BA 0 mcg
250 mcg
CB
A 250
125
0 mcg mcg
mcg
DC
B 125
250 mcg
62·5 mcg
mcg
ED
C 62·5
125
31·3 mcg mcg
mcg
E
D
Answer 31·3 mcg
62·5 mcg
Answer
E A 31·3 mcg B C D E
AnswerA
O OB C
O D
O E
O
O
A O
B O
C O
D O
E
O O O O O
PHAR1001 Mathematics Tutorial Workbook April 2014
PHAR1001 Mathematics Tutorial Workbook April 2014
PHAR1001 Mathematics Tutorial Workbook April 2014

65
3 Scientific Calculations 71
3 Scientific Calculations 71
Indicate the correct answer.
Test yourself
3 Scientific Calculations Digoxin is removed from the human circulation with a half- 71
Indicate the correct answer.
Test yourself Q84 life of
Digoxin about 2 days.
is removed Whatthe
from is the
humanfirst-order rate
circulation constant for
with a half-
Indicate the correct answer.
Test yourself Q84 this
life process?
of about
Digoxin
(Ln (2) =
2 days. from
is removed
0·6931
Whatthe ).
is the
humanfirst-order rate
circulation constant for
with a half-
this process? (Ln (2) = 0·6931 ).
Q84 life of about 2 days.
A 2·88 day−1
What is the first-order rate constant for
this process? (Ln −1(2) = 0·6931).
B
A 0·68 day−11
2·88 day
C 0·34 day −1
B
A 0·68 day−11
2·88 day
D
C 0·34 day−1
0·34 day
B 0·68 day −1
E
D 0·00068
0·34 day day
C 0·34 day 1
Answer −1
E
D 0·00068
0·34 day day
A B C D E
Answer
E 0·00068 day−1
AnswerO
A O
B OC O
D O
E
O
A the correct
Indicate O
B answer. O C O
D O
E
Test yourself HCl O
is consumed O inanswer. O
a first-order O
reaction. GivenOthe rate
Indicate the correct
Test yourself
Q85 constant
HCl of the
is consumed reaction is
inanswer.0·693 min −1
what is the half-life
a first-order reaction. Given of
the rate
Indicate the correct
Test yourself
Q85 HCl? (Lnof(2)
constant
HCl is consumedthe =reaction
0·6931is) 0·693 min−1 what is the half-life of
in a first-order reaction. Given the rate
HCl? (Lnof(2)the =reaction
0·6931is) 0·693 min−1 what is the half-life of
Q85 constant
A 1 min
HCl? (Ln (2) = 0·6931)
B
A 11 smin
C
B 11 hr
A 1 smin
D
C 11 hr
s
B 1s
E
D 111 hr
syr
C
Answer 1 yr
E
D 1s
A
Answer 1 yr B C D E
E
O
A
Answer O
B O
C O
D O
E
O
A the correct
Indicate O
B answer. O C O
D O
E
Test yourself Upon Ostorage, O answer. O denaturesOaccording to
Erythropoeitin O a first-
Indicate the correct
Test yourself
Q86 order process.
Upon storage, After 3 days
Erythropoeitin atdenatures according todrug
60 °C, 50 % of the has
a first-
Indicate the correct answer.
Test yourself
Q86 been
order
Upon
degraded.
process.
storage,
Under3 days
After these atconditions,
Erythropoeitin 60 °C, 50
denatures
how
% ofmuch remains
thetodrug
according has
a first-
after
been one month?
degraded. Under these conditions, how much remains
Q86 order process. After 3 days at 60 °C, 50 % of the drug has
after
been one month? Under these conditions, how much remains
degraded.
A 0·01 %
after one month?
B
A 0·1 %%
0·01
C
B 10·1
%%
A 0·01 %
D
C 12
1 %%
B 0·1 %
E
D 25 %
12
C 1 %%
Answer
E 25 %
D 12 %
AnswerA B C D E
E 25 %
AnswerO
A O
B O
C OD OE
O
A O
B O
C O
D 2014 O
E
PHAR1001 Mathematics Tutorial Workbook April
O O O O O
PHAR1001 Mathematics Tutorial Workbook April 2014
PHAR1001 Mathematics Tutorial Workbook April 2014

66
NO CALCULATOR NEEDED
Again, it looks hard but there is a simple way to get to the truth:

0 days elapsed = 100 % remains

3 days elapsed = 50 % remains
6 days elapsed = 25 % remains
9 days elapsed = 12.5 % remains
12 days elapsed = 6.25 % remains
15 days elapsed = 3.125 % remains
18 days elapsed = 1.5625 % remains
21 days elapsed = 0.78125 % remains
24 days elapsed = 0.390625 % remains
27 days elapsed = 0.1953125 % remains
30 days elapsed = 0.09765625 % remains

… so almost none (and those numbers are real). But that’s hard work because of the number of
times you have to divide by 2 …

NO CALCULATOR NEEDED
There is another, easier way to do business — which is to recognise that the concentration is
halved by each half life and therefore to calculate the fraction of the original that remains:

time
number of half lives elapsed =
half-life
30 days
=
3 days
= 10

original amount
∴ amount remaining =
2(number of half lives)
100 %
=
210
100 %
=
1024
100 %
≈
1000
≈ 0.1 %

67
 6 days = 25 %
9 days = 12·5 % ...
27 days = 0·195 %
30 days = 0·097 ... almost none (and those numbers are real!)

Indicate the correct answer.

Test yourself In aqueous solution, Drug A denatures according to a first-
Q87 order process. After 1 day at 20 °C, 50·0% of the drug has
been degraded. Under these conditions, how much remains
after one week?

A 0·2 %
B 6·3 %
C 13 %
D 8·0 %
E 0·8 %

Answer
A B C D E
O O O O O

Indicate the correct answer.

Test yourself In aqueous solution, Drug A denatures according to a first-
Q88 order process. After 1 day at 20 °C, 50·0% of the drug has
been degraded. What is the first-order rate constant for this
process of degradation? (Ln (2) = 0·6931).

A 0·6931 day −1
−1
−1
B 1·54 hr−1
−1
C 1·0 day−1
D 0·5 day−1
−1

E 11 day−1
−1
0·6931
0·6931

Answer
A B C D E
O O O O O

PHAR1001 Mathematics Tutorial Workbook April 2014

April 2014

68
 3 Scientific Calculations 73

3.5.2 Zero order kinetics

We4.2.ZERO-ORDER
have seen that first-orderKINETICS
kinetics apply when the rate of a process is directly proportional to

W
an element being consumed by that process. For example, where the rate of degradation of a
e have seen that rst-order kinetics apply when the rate of a process is directly proportional to an element
drug is proportional to the quantity of drug remaining (to the power of 1) this is termed a first-
being consumed by that process. For example, where the rate of degradation of a drug is proportional to
order decay.
the concentration of drug remaining (to the power of 1) this is termed a rst- order decay.

The term
The term zero-order
zero-order appliesapplies
when when
the rate theofrate of the process
the process is independent
is independent of the elements
of the elements being
being consumed
consumed by that process … i.e. it remains a constant. Such zero-order processes are so-called
by that process ... i.e. it remains a constant. Such zero-order processes are so-called because they are directly
becausetothey
proportional are directly proportional
the concentration of, say, a drugtobeing
the concentration
degraded to theof, say, of
power a drug being degraded
zero (remember to the
that anything
raisedpower
to theof zero is 1). that anything raised to the power of zero is 1).
zeroof(remember
power

Zero-order kinetickinetic
Zero-order pro lesprofiles
always yield a straight
always yield aline of the line
straight form:of the form:

Concentration of drug vs. time

100

80
Drug Concentration / %

60

40

20

0
0 5 10
T

Figure 3.2 Zero-order decay kinetics.

Figure 3.2 Zero-order rate kinetics

As before,
As before, the ratethe ratereaction
of the of theatreaction
any timeis givenbybythethe
is given gradient
gradient of line
of the theatline. Because
that point. the the
Because lineline
is is
straight, the rate of the process remains unchanged as the concentration of drug changes.
straight, the rate of the process remains unchanged as the concentration of drug changes. That is to say that the
rate of concentration decline is constant.

PHAR1001 Mathematics Tutorial Workbook April 2014

WHY IS THIS ZERO-ORDER?
Mathematically we would write:

dy
− ∝ y 0 ∝ 1 (so a constant)
dx
rate of reaction ↑ ↑ the concentration of reactant remaining

Thus the reaction proceeds at a rate proportional to the concentration of reactant to the power
of 0 ... hence zero order.
69
fi
fi
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Alternatively, we may write:

dy
− = a constant = m
dx
where: y = m x + c

… which, of course, is he equation for a straight line.

Such zero-order processes are far less common than rst-order processes. They are encountered in chemical
reactions where access to (for example) the surface of a catalyst is the rate-limiting factor in a reaction ... under
these circumstances, the surface of the catalyst is always saturated with (excess) reactant(s).

dy
WHY HAS IT BEEN WRITTEN − ?
dx
dy
− ∝ y 0 ∝ 1 (so a constant)
dx
noting the minus sign ↑

(dx)
dy
The minus sign is a mathematician’s reminder that the slope of the graph is negative (the

line goes downwards from left to right). This is a useful reminder but mathematically unnecessary
it is equally true to say:

dy
∝ y0
dx
noting that ↑ is the proportionality symbol, not an equals sign.

because it is true to say:

dy dy
=−1×−
dx dx
∎

Zero-order processes are also encountered in certain drug release events. For example, the di usion of drug into
the skin from a transdermal patch formulation is frequently zero-order, or very close to it ... yielding a time-
independent rate of (say) nicotine delivery.

70
fi
ff
the diffusion of drug into the skin from a transdermal patch formulation is frequently zero-order
... yielding a time-independent rate of (say) nicotine delivery.

Indicate the correct answer.

Test yourself In aqueous solution, Drug B denatures according to a zero-
Q89 order catalytic process. After 1 day at 20 °C, 50·0% of the
drug has been degraded. After a further 12 hours, how much
of the drug remains?

A 0·12 %
B 1·2 %
C 12 %
D 25%
E 20 %

Answer
A B C D E
O O O O O
3 Scientific Calculations 75
3 Scientific Calculations 75
Indicate the correct answer.
Test yourself Drug X theis delivered transdermally at a zero-order rate of
Indicate correct answer.
Test yourself
Q90 24 mcg hr −1
. How much will be absorbed
Drug X is delivered transdermally at a in 5 hours? rate of
zero-order
Q90 −1
24 mcg hr . How much will be absorbed in 5 hours?
A 240 mg
B
A 120 mg
240 mcg
C
B 10
120mg mcg
D
C 1200
10 mgmcg
E
D 5 mg mcg
1200
PHAR1001 Mathematics
Answer Tutorial Workbook April 2014
E 5 mg
A
Answer B C D E
O
A O
B O
C O
D O
E
O the correct
Indicate O answer. O O O
Test yourself Drug Y the
is delivered transdermally at a zero-order rate of
Indicate correct answer.
Test yourself
Q91 50 mcg
Drug
−1
Yhris delivered
. How much will be absorbed
transdermally in 2 days? rate of
at a zero-order
Q91 −1
50 mcg hr . How much will be absorbed in 2 days?
A 2·4 mg
B
A 1·2 mg
2·4 mg
C
B 3·6
1·2 mg
mg
D
C 1200
3·6 mgmcg
E
D 5 mg mcg
1200
Answer
E 5 mg
A
Answer B C D E
O
A O
B O
C O
D O
E
O the correct
Indicate O answer. O O O
Test yourself Drug Z the
is degrades by a zero-order process at a rate of
Indicate correct answer.
Test yourself
Q92 0·1 −1
Drug Z is degrades by isa packaged
mg yr . If the drug zero-orderin process
unit doses
at of 10 mg
a rate of,
what
0·1 mgpercentage of the stated dose remains after 3 years?
Q92 yr−1. If the drug is packaged in unit doses of 10 mg,
what percentage of the stated dose remains after 3 years?
A 87 %
B
A 90 %
87 %
C
B 92
90 %
%
71
D
C 95 %
92 %
E
D 97 %
95 %
Answer
E 97 %
 E 5 mg
Answer
A B C D E
O O O O O
Indicate the correct answer.
Test yourself Drug Z is degrades by a zero-order process at a rate of
Q92 0·1 mg yr−1. If the drug is packaged in unit doses of 10 mg,
what percentage of the stated dose remains after 3 years?

A 87 %
B 90 %
C 92 %
D 95 %
E 97 %
Answer
A B C D E
O O O O O

PHAR1001 Mathematics Tutorial Workbook April 2014

ANSWERS FOR PART 3 PUZZLES

60. E 70. C 80. E

61. B 71. E 81. E

62. A 72. C 82. B

63. C 73. A 83. D

64. E 74. B 84. C

65. D 75. E 85. A

66. E 76. D 86. B

67. C 77. C 87. E

68. A 78. D 88. A

69. C 79. A 89. D

90. B

91. A

92. E

72