General Certificate in Brewing

Section 1.4 Mash Conversion

General Certificate in Brewing | Revision 2015

BRILLIANT BEER COMPANY

Revision 2015
Authored by: Tim O’Rourke
Brilliant Beer College 2015 ©
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 General Certificate in Brewing

Section 1.4 Mash Conversion

Summary of knowledge required for this section.
Ref. Topics Candidates should understand and be able to
: (Number of questions explain and describe in simple terms, or demonstrate
to be answered = 5)
familiarity with
1.1 Definition of beer and 1. A generic, non-legalistic definition of beer in terms of
types of beer its typical ingredients and methods of production.
2. Characteristics which differentiate lagers, ales and
stouts.
1.2 Barley and malt 1. The role of barley as a principal source of starch.
2. The special attributes of barley for malting.
3. The significant changes that occur when the barley
grain is malted.
4. The principal constituents of malt.
5. The key malt parameters of degree of modification,
extract content, moisture content, extract, and
colour.
6. The selection of malt for beer type and mash
conversion method.
7. Pre-acceptance checks at malt intake.
1.3 Adjuncts and 1. Reasons for the use of adjuncts.
2. Types of adjunct and their method of use.
coloured malts 3. Typical usage rate as proportion of the grist.
4. Types of coloured malt and their characteristics
5. Typical uses of coloured malts.
1.4 Mash conversion 1. The respective roles of the amylases and protease,
the effect of temperature, pH and time on their

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activity.
2. Temperature and wort viscosity.
3. The influence of the ionic composition (hardness
salts) of mashing liquor (water) in the mash and on
beer flavour.
4. The starch test.
5. Key sweet wort parameters of fermentability,(see
also section 10.2).
1.5 Grist composition 1. The extract yield of raw materials.
2. Malt and adjunct quantities required for a grist from
and extract theoretical material extract values.
performance 3. Calculation of brewhouse extract performance.

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KEY LEARNING OUTCOMES: On completion of this unit the student will be able to:
 Explain how enzymes work
 Describe the main enzymes pres ent n malt
 Understand how starch is broken down during mashing
 Understand the role of mash thickness, pH and temperature on starch
hydrolysis
 Know how to perform the iodine test
 Understand the key changes which occur during mashing and how they
affect beer quality.

Mashing
The malting process is critical in making the barley suitable for starch breakdown (conversion)
during the mashing stage.

Difference between barley and malt

Nature of barley Nature of Malt

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In barley the starch granules are in a During malting the beta glucan cell walls
protein matrix surrounded by cell walls and most of the protein matrix is broken
made from beta glucan down exposing the starch granules to
hydrolysis

There is only a limited amount of During malting all the enzymes necessary
enzymes present in the barley corn to hydrolyse the starch are produced and
survive gentle kilning

Mashing is a critical process in wort production. The main objective of mashing is to allow
the conversion of starch from the malt and solid adjuncts into fermentable and non-
fermentable sugars to produce wort of the desired composition.

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 The amount and quality of the extract achieved is important. We want to minimise certain
compounds such as tannins from the husks, but other compounds are desirable, such as
certain sugars and protein degradation products.

In Mashing crushed malt (grist) is mixed with brewing (product) water at a specific
temperature and ratio to the grist (see table 1.4.2) to allow the malt enzymes to convert the
accessible starch into fermentable sugar.

Under appropriate conditions mashing may continue the breakdown of proteins and beta
glucan molecules into more soluble forms. This is a continuation of the malting process,
particularly when using less well modified malts, and is required to continue to break down
the protective beta glucan cell walls making the starch more accessible.

Biochemical Changes
The major biochemical changes which occur during mashing are catalysed by naturally
produced enzymes in barley during the germination process. A degree of structural
breakdown of the endosperm takes place during malting, which is measured as
modification of the malt. Enzyme production and malt modification are then halted by
kilning, and the enzymes are subsequently released to complete their activity during the
mashing process.
Enzymes are biological catalysts which work by lowering the
energy required for specific reactions to occur. They are complex
molecules with a very intricate three dimensional structure, which
is integral to their mode of action. If the structure is destroyed
then the enzymes lose their ability to catalyse the reaction.
How enzymes work
 Enzymes work by helping normal reactions to occur at much lower temperatures
than would normal.
 Enzymes are present in all living organisms helping
metabolism.

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 Barley enzymes are designed to release the nutrients stored
in the barley corn allowing the plant to grow and germinate. The
Brewer wants to accelerate these reactions, so that the
hydrolysis of starch contained in the barley endosperm, which
takes a few weeks in nature, can be completed in less than one
hour in the mash tun.
Enzymes are biological catalysts and are affected by the conditions in which they work
particularly temperature and acidity (pH).
There are three principal enzyme reactions which are important during mashing:
 Enzymes which degrade starch and polysaccharides
 Enzymes which degrade gums such as beta-glucans and pentosans
 Enzymes which brake down of proteins and polypeptides

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 There are two principal effects of
temperature:
As with any reaction the higher the
temperature the faster the rate of
reaction.
Arrehenius states that for every 10 C
degree rise in temperature there is a
doubling in the rate of reaction.
However enzymes are quite delicate and
rely on a complex three dimensional
structure for their activity.
Increase temperature causes damage to
this structure and effectively
permanently denatures the enzymes so
it loses all its activity.
All enzymes have different abilities to withstand temperature effects depending on their
internal chemical structure. Enzymes are able to work below their optimum temperature
slightly more slowly, but once the optimum is exceeded they rapidly denature and lose
their activity.
Table showing typical optimum temperatures for selected malt based enzymes
Enzyme Optimum Temperature Effect
C
Alpha amylase 68 – 72 Liquefy starch
Beta amylase 63 – 65 Produce maltose sugar
Limit dextrinase 50 – 55 Break down branched
starch
Protease 45 – 50 A range of enzymes

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hydrolyse proteins &
polypeptides
Beta glucanase 40 - 45 A range of beta glucan
enzymes break down the
endosperm beta glucan cell
walls surrounding the starch
granules
Mashing below 60C allows the beta glucanase and proteases to continue to break down
the endosperm cell structure. Before the enzymes can break down the starch it has to
be gelatinised, which for malt and barley occurs around 60C, since Limit Extinase which
is a de-branching enzyme is denature above 60C it plays little part in normal mashing
and the branch branched starch residues (the malto dextrins) persist into the finished
beer.

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The difference in temperature sensitivity between beta amylase (63 – 65 C) and alpha
amylase (68 – 72 C) can be used to control the fermentability (the final gravity of the
beer) by controlling the mash stand times and temperatures.

Changes in pH will affect the three dimensional

of the enzymes leading to a change in the
delicate three dimensional structure of the
enzymes and hence a loss of their activity.
When the pH returns to the optimum the level of
enzyme activity will be restored.

Table showing typical optimum pH for selected malt based enzymes

Enzyme Optimum pH Effect
Alpha amylase 5.3 – 5.8 Liquefy starch
Beta amylase 5.4 – 5.6 Produce maltose sugar
Limit dextrinase 5.0 – 5.5 Break down branched
starch
Protease 4.5 – 6.0 A range of enzymes
hydrolyse proteins &
polypeptides
Beta glucanase 4.7 – 5.0 A range of beta glucan
enzymes break down the
endosperm beta glucan cell

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walls surrounding the starch
granules
The optimum range of conditions for an enzyme can be extended by external factors such
as mash thickness (water to grist ratio) and ionic composition (particularly Ca 2+ ions).
The rate of reaction will also be affected by the concentration of substrate, which in mash
is usually in excess. The enzyme concentration is measured by diastatic power of the
malt.
Starch hydrolysis
The principal enzymes involved in the hydrolysis of starch to sugars are alpha-and beta-
amylase. Before enzyme hydrolysis can occur it is necessary to open up the starch
granule by exceeding the starch gelatenisation temperature, which for malted barley is
above 600C, rendering the starch accessible to enzymic attack. It is also necessary to

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 select the optimum conditions for saccharifying enzymes by::
 Optimising pH of the mash (usually between pH 5 and 6)
 Adding calcium ions to stabilise the enzyme
 Using thick mash (high concentration of substrate to insulate the enzymes
against denaturing)
 Optimising temperature to favour the activity of both the alpha and beta-amylase.
The amylase enzymes are able to hydrolyse the alpha -1,4 links in amylose and
amylopectin to produce a mixture of glucose, maltose, maltotriose and higher molecular
weight un-fermentable sugars, called dextrins, to produce an all malt wort (sugar solution
derived from) with around 75 - 80% fermentability.
There are two types of Starch
Amylose Amylopectin

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Amylose are straight chains of glucose Amylopectin which is a series of glucose
molecules linked by alpha 1-4 bonds molecules in a line linked through alpha 1-4
and accounts for 20-30% of the total bonds but around every 27 glucose units
starch in the grain there are branched links of alpha 1-6 bonds
and this accounts for around 70-80% of the
total starch in the grain.
Starch is a series of glucose molecules principally linked through alpha 1-4 bonds but in
Amylopectin around every 27 glucose units there are branched links of alpha 1-6 bonds.
Amylopectin accounts for around 70-80% of the total starch in the grain. the starch
hydrolysing enzymes alpha and beta amylase can only break the basic alpha 1-4 bonds
but in Amylopectin around every 27 glucose units there are branched links of alpha 1-6,
which cannot be hydrolysed under normal mash conditions leaving branched more
complex sugars behind called malto dextrins which are not fermentable

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A

diagrammatic representation of hydrolysis of starch (amylase) by amylase enzymes.

Alpha and beta amylase enzyme attacks the starch in a different way and have different
optimal operating conditions:

With amylose (un branched starch

molecules) can be fully hydrolysed by
the beta amylase which will split off pairs
of glucose molecules (called maltose)
from the non reducing ends.
Alpha amylase breaks the amylose
chain in the centre (endo –enzyme) at
random reducing the chain length and

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making more reducing ends for the beta
amylase to break down. increasing the
rate of starch breakdown.
Beta amylase breaks the chain from the
non-reducing end of the starch chain
(exo enzyme) to produce maltose sugar.
Its activity will continue until it reaches
the branch point when it is halted.

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 The difference in action has a different effect on a starch solution:
 Beta - amylase produces simple sugars (maltose) – saccharification enzyme
 Alpha- amylase randomly hydrolyses starch reducing viscosity – liquefying
enzyme
With complex starch molecules eg amylopectin, beta amylase can only hydrolyse the
pairs of glucose molecules (maltose) until it reaches a branched 1-6 link, which it cannot
pass. The effect of alpha amylase is to break the chains in the middle exposing further
ends to beta amylase attack. Neither enzyme can break the alpha 1-6 links leaving chunks
of carbohydrates comprising 4 or more glucose units called maltodextrins which are
unfermentable and give beer its texture and mouthfeel.
The range of sugars produced during conversion determines the fermentability of the wort.
If the enzyme attack is complete, the wort will be very fermentable. If the enzyme attack is
incomplete, the wort will be only partially fermentable.

Table of are optimum conditions for mashing

Condition Low Optimum High

Temperatur Low temperatures do not affect 65C High temperatures inactivate

e. the enzymes much, but the enzymes including a and ß
starch must be gelatinised first. amylases.
Gelatinisation temperature for The action of amylases is stopped
malt starch is below 65C. at temperatures over 70C.

pH. Acidic conditions kill the 5.4 High pHs slow enzyme action, but
enzymes. Enzyme action is it does continue at pHs of 7 or
stopped at pHs below 5.0 above.

Enzymes are more sensitive to Between 2.5 Enzymes are less sensitive to heat

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heat in a thin mash. and 3.5 litres in a thick mash. There is a higher
Water.
of water per concentration of enzyme and
There is a lower concentration of
(Mash kilogram of starch in a thick mash.
enzyme and starch in a thin
thickness) dry grist.
mash.

Time. Enzymes take time to attack the 30 minutes
starch. Conversion will be
incomplete in less than 30
minutes.
Conversion will be virtually
complete after 30 minutes. A
longer time will not increase the
yield of sugar but may increase
fermentability

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Starch end point
At the end of mash conversion it is necessary to check if all the starch has been
converted (broken down to simple sugars and dextrins).

Iodine forms a blue black colour in the presence of starch

Amylose in starch is responsible for the formation of a deep blue

colour in the presence of iodine. The iodine molecule slips inside of
the amylose coil.

Iodine is not very soluble in water, therefore the iodine reagent

is made by dissolving iodine in water in the presence of
potassium iodide. This produces the linear tri-iodide ion
complex which is soluble and can stain the amylase.

Starch – blue black colour

No starch – colour stays orange or yellow.

The starch end point test is a useful quality
technique to confirm that full conversion has
occurred..

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Practical work – make up a solution of Iodine and test a sample of mash at the start of
mashing and a sample of mash at the end of mashing and observe the difference.
Beta-glucan breakdown.
As well as starch based oligosaccharides, there are a number of non-starch barley
polysaccharides, the most significant of which is beta-glucan which makes up more than
75% of the cell wall. . The molecule has a distinctive linear structure in with roughly 70%
beta1,4 linkages and 30% beta1,3 linkages.

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Structure of alpha and beta links in carbohydrates.
Most beta-glucan is water soluble, but a
proportion is bound covalently to cell wall
proteins. If there is insufficient degradation of the
cell walls, then enzymic access to the protein and
starch will be restricted, and the extract from the
malt reduced.
Although much of the necessary beta-glucanase
activity occurs during malting, there is inevitably
some survival of cell wall material (even in the
most fully modified malt), and this will be
exacerbated if adjuncts such as barley and wheat
are also used; consequently it is necessary to
ensure the continued activity of beta-glucanase
during mashing, since more beta-glucan will
released into the wort by the activity of beta-
glucan solublilase which is more heat stable than the malt beta-glucanase which breaks
down the beta-glucan structure, and it is common practice in many breweries to add
exogenous beta -glucanase to decrease wort and beer viscosity and to improve
filterability.
Hydrolysis of Proteins and Polypeptides
Proteins are made up of amino acid molecules which all conform to the same basic
structure.

→
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Proteolysis is the term used to describe enzymic action that breaks down of
proteins into simpler soluble forms such as amino acids.

The method proteolytic enzymes use to breakdown proteins is similar to that of the starch
breakdown enzymes except that the optimum temperature for proteolitic enzymes is
around 50°C.
In well modified malts most of the proteolysis has occurred during malting leaving the
starch breakdown during mashing. While around While about 95% of the starch from

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malt is solubilised by the end of mashing, only about 35 - 40% of the malt protein (TN -
total nitrogen) is solubilised. This is referred to as the TSN (total soluble nitrogen) in an
un-boiled wort.
This ratio is used to determine the amount of cell wall breakdown or modification and is
expressed as the Soluble Nitrogen Ratio, SNR (also called Kolbach index when
calculated from a Congress Mash).
SNR = Total soluble nitrogen in the wort/Total nitrogen (from the barley) x 100
(this measurement is describe in malt analysis section 1.2 on malt analysis)
Less well or under-modified malts require a proteolysis stand (usually around 50C) to
break down the proteins matrix and beta glucan cell walls. Mashes with undermodified
malt, for example lager malt, allows for this by having a low temperature stand for the
proteolytic enzymes to work, followed by a ‘saccharification’ stand for the starch enzymes
to work.
The importance of nitrogenous substances in beer is indicated in the table:

Action Relevant Nitrogen Compounds

1. Yeast welfare Amino acids and lower molecular weight products

2. Palate All compounds

3. Foam Higher molecular weight products (alkaline)

4. Haze and
Higher molecular weight products (acidic)
stability
5. pH Amino acids

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Mashing Techniques
The different mash profiles for different beer styles (and malt specifications) are shown
below:

Isothermal (single temperature) mash profile

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Well modified malt does typically used in ale brewing not require a proteolytic stand and
can be mashed in at one temperature of around 65 C which is the optimum compromise
temperature for scarification (producing sugars) using the malt enzymes alpha and beta
amylase.

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Programmed infusion mashing

When using less well modified malt typically used in lager brewing use a step
temperature rise starting off with a proteolytic stand around 50C before being heated to

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around 65 C which is the optimum compromise temperature for scarification (producing
sugars) using the malt enzymes alpha and beta amylase.

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Decoction Mash
Another technique used by lager brewers is decoction mashing, where a portion of
the mash is removed and boiled in a separate vessel (mash cooker) before being
added back to the main mash, thereby raising the combined temperature of the mash.

This process is particularly appropriate when using very poorly modified malt as boiling
part of the mash helps to extract and convert the available starch increasing extract
recovery.

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Other materials broken down or extracted from the malt.
During mashing many other malt components are digested into smaller molecules. In
particular lipids and polyphenols. A prolonged mash stand will extract more of these
compounds.
The compounds have the following properties in wort and beer.
Lipids
Usually < 2% of total lipid in grist is dissolved in to the wort, however rapid wort
separation and low cut off gravities can give rise to elevated lipid levels in wort. Lipids
contribute to stale flavours and poor foam performance in the packaged beer.
Polyphenols
Polyphenols from the malt leach in to wort. The amount of polyphenols extracted
increases with increasing pH and sparge temperature. Oxidisable polyphenols pass
through to beer and can then give rise to hazes with proteins-to limit these in wort avoid
last runnings. The react with proteins to produce first chill haze and then permanent
haze.When oxidised give harsh astringent flavours to beer often associated with the
ageing process.

Minerals
Organic phosphates in malt are degraded by phosphatases to phosphoric acid and hence
mash pH is lowered. Wort is not normally deficient in any mineral needed to support yeast
growth with the exception in some cases of zinc
The ions in to which mineral salts dissociate have a profound effect on the composition
of wort
 Influence mash pH
 Act as buffers

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 Influence the extraction of proteins and vitamins
 Affect the stability of enzymes
 Affect beer flavour:
o Chloride-full
o Sulphate-dry
o Lactate-soft
Contamination by some mineral ions such as copper and iron can inactivate enzymes
and they are toxic to yeast.

Calcium ions stabilise alpha-amylase enzymes and precipitate phosphates thus lowering
mash pH in a beneficial.

Temporary hardness from carbonate and bicarbonate is harmful in mashing-pH is raised

as these substances act as weak bases. Carbonates and bicarbonates can be removed

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before mashing or their effects countered by addition of acid or calcium salts to lowers
mash pH.
(Water treatment, pH and mineral salts are covered in Section 18).

Summary of the importance of the mashing process

The Mashing Process determines:

 Alcohol content of beer
 Concentration of unfermented sugar in beer
 Peptide and amino acid profile of the wort
 Yeast nutrients for robust fermentation
 Buffering capacity and pH of the wort
 Β-glucan content of the beer
 Efficiency of malt extraction
 Physical properties of the beer (foam, colour, clarity)

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