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8]VeiZg , METALS AND

REACTIONS
Introduction
Metals differ in their reactivity with other chemicals such
as air, water and acids. Some metals such as sodium are
so reactive that they cannot exist as the free element in
nature. Gold is so unreactive that native gold is commonly
found in natural deposits. The reactivity of metals
influences their uses. Reactivity is a chemical property
that will be examined in this section.

In this chapter
7.1 Metals and their reactivity page 128
7.2 Reactivity and uses of metals page 132

Figure 7.1
Sodium must be stored away from air and water as it
is a very reactive metal.
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Remember Reactions of metals
Before beginning this section, The reactivity of metals can be determined
you should be able to:
• explain the relationship experimentally by observing the speed
between the reactivity of an of reaction of the metals with common
element and the likelihood of
it existing as an uncombined chemical reagents such as water, oxygen
element. and dilute acids.
Key content
By the end of this section, you Reaction with water
should be able to: Results of experiments to compare the
• describe observable changes
when metals react with dilute reactions of a selection of common metals
acid, water and oxygen with water, hot water and steam are shown
• describe and justify the
criteria used to place metals in table 7.1. It shows that either oxides or
into an order of activity based hydroxides are formed.
on their ease of reaction with
oxygen, water and dilute acids
• identify the reaction of metals Table 7.1 Reactivity of metals with water
with acids as requiring the
transfer of electrons K, Na, Ca react with cold water to form
• perform a first-hand hydroxide ions and release
investigation incorporating hydrogen gas
information from secondary
sources to determine the
metal activity series Mg reacts with hot water to form
• construct word and balanced hydroxide ions and release
chemical equations for the
reaction of metals with water, hydrogen gas
oxygen and dilute acid
• construct half-equations
to represent the electron Al, Zn, Fe react with steam at red heat to
transfer reactions occurring form oxide ions and release
when metals react with hydrogen gas
dilute hydrochloric and dilute
sulfuric acids Figure 7.2 Magnesium burns
• present information by using Sn, Pb, Cu, no reaction brightly in air or oxygen.
symbols and formulae to Hg, Ag, Au
express relationships and
using appropriate units for
physical quantities. The reaction rate is highest for active metals. Unreactive metals such
as copper and gold do not react; they are inert. Potassium, sodium and
calcium are the most reactive metals with water. The following equations
inert: describes a substance
that does not react with other illustrate some of the reactions described in table 7.1.
substances • Sodium + water
Word equation:
sodium metal + water sodium hydroxide solution + hydrogen gas
Balanced chemical equation:
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)
• Iron + steam
Word equation:
iron metal + steam iron oxide solid + hydrogen gas
Balanced chemical equation:
Fe(s) + H2O(g) FeO(s) + H2(g)
Figure 7.3
Magnesium reacts with hot water, forming bubbles of hydrogen gas on its surface.

128 METALS
Reaction with oxygen
Experiments can be conducted to observe the reaction of metals with air
(21% oxygen). The metals are normally heated (e.g. in a Bunsen flame)
to initiate the reaction. The hot metals can also be plunged into gas jars of
oxygen. The results of such experiments are shown in table 7.2.

Table 7.2 Reactivity of metals when heated in air or with oxygen

peroxide: a compound containing K, Na, Ca burn rapidly to form oxides or peroxides


the peroxide radical O22–
Mg, Al, Zn, Fe burn readily if powdered or as fine fibres to form oxides

Sn, Pb, Cu, Hg become coated with oxide layers during heating

Ag, Au no reaction

Potassium, sodium and calcium are highly reactive to oxygen while silver
and gold are unreactive. The following equations illustrate some of the r
eactions in table 7.2.
• Calcium + oxygen
Word equation:
calcium metal + oxygen gas calcium peroxide solid
Balanced chemical equation:
Ca(s) + O2(g) CaO2(s)
• Mercury + oxygen
Word equation:
mercury metal + oxygen gas mercury (II) oxide solid
Balanced chemical equation:
2Hg(s) + O2(g) 2HgO(s)

Reaction with dilute acids


The reaction of metals in dilute solutions of hydrochloric or sulfuric acid
has been determined and the results are shown in table 7.3.

Table 7.3 Reactivity of metals with dilute acids

K, Na effervesce very rapidly producing hydrogen gas, which


may ignite

Ca, Mg bubble rapidly releasing hydrogen

Al, Zn, Fe, Sn, Pb bubble moderately to very slowly as hydrogen is released;
Figure 7.4 reaction is faster in warm acid; lead stops reacting when
Calcium burns in oxygen with coated with insoluble PbCl2 or PbSO4
a bright white flame.
Cu, Hg, Ag, Au no reaction

The reactive metals, such as potassium and sodium, often cause


explosions because the reaction releases both heat and hydrogen. The
surface of aluminium must be cleaned or the oxide coating will prevent
reaction until it is dissolved away by the acid. Heating the acid increases
the reaction rate.

CHAPTER 7 METALS AND REACTIONS 129


The following equations illustrate some of the reactions in table 7.3.
• Sodium + dilute sulfuric acid
Word equation:

sodium metal + sulfuric acid sodium sulfate solution + hydrogen gas

Balanced chemical equation:

2Na(s) + H2SO4(aq) Na2SO4(aq) + H2(g)

• Zinc + dilute hydrochloric acid


Word equation:

zinc metal + hydrochloric acid zinc chloride solution + hydrogen gas

Balanced chemical equation:

Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)

The activity series of metals


The experiments described in the previous section reveal a common
trend in the reactivity of metals. The order of metal reactivity is known as
the activity series of metals. A more complete list is shown in table 7.4.
The activity series is the combined Table 7.4 Activity series of metals
result of many other experiments
including thermal decomposition most active potassium
reactions of compounds of these sodium
Figure 7.5 elements. Care must be taken in using
Zinc reacts with hydrochloric acid barium
this list as some metals can behave
producing bubbles of hydrogen gas. unexpectedly in different chemical calcium
environments. For example, aluminium magnesium
is more reactive than iron yet it does not
corrode as rapidly as iron. This is due aluminium
to an impervious coating of aluminium chromium
oxide that exists as a microlayer on the
zinc
surface of that metal.
iron
Reactivity and electron transfer cobalt
The reaction between metals and acids
nickel
or other chemicals involves electron
transfer. tin
• The more reactive a metal, the lead
more readily electron transfer
copper
occurs. Thus, magnesium rapid-
ly reacts with dilute hydrochloric mercury
acid as magnesium rapidly trans- silver
fers electrons to the hydrogen ions
in the acid. This process can be platinum
summarised using half-equations that least active gold
show the process of electron loss
by the metal and electron gain by the hydrogen ion. The over-
all equation is found by summing the two half-equations and
cancelling out the electrons.

130 METALS
Electron loss: Mg(s) Mg2+(aq) + 2e–
Electron gain: 2H+(aq) + 2e– H2(g)

7.1 PRACTICAL Ionic (overall) reaction: Mg(s) + 2H+(aq) Mg2+(aq) + H2(g)


ACTIVITIES Atoms of noble metals, such as gold, hold their valence electrons tightly
The activity series and do not transfer them to the hydrogen ions of the acid. Thus, there is
of metals no reaction between these metals and dilute hydrochloric acid.

SYLLABUS FOCUS
11. WRITING HALF-EQUATIONS AND IONIC EQUATIONS
Half-equations help us understand the electron transfer process between
metals and non-metals. Generally:
• metals lose electrons to form metal ions (cations)
• non-metals gain electrons to form non-metal ions (anions)
• hydrogen ions gain electrons to form hydrogen gas.
Using these generalisations, we can write half-equations for the reactions
between metals and dilute acids. Half-equations must be balanced in
terms of atoms and charges.
Ionic equations are created by summing two half-equations so that the
number of electrons lost by the metal equals the number of electrons
gained by the non-metal or hydrogen ion.
Example: Reaction of aluminium with hot sulfuric acid
Aluminium atoms will lose three electrons and the hydrogen ions will
gain two electrons.
Electron loss: Al(s) Al3+(aq) + 3e– (1)
Electron gain: +
2H (aq) + 2e – H2(g) (2)
To balance the electrons, multiply half-equation (1) by 2 and half-
equation (2) by 3, and then add the two half-equations. Check that the
atoms and charges balance.
Electron loss: 2Al(s) 2Al3+(aq) + 6e–
Electron gain: 6H+(aq) + 6e– 3H2(g)
Ionic equation: +
2Al(s) + 6H (aq) 2Al3+(aq) + 3H2(g)

7.1 QUESTIONS 3. Identify the metal from the following


list that does not react with steam at red
heat but does react slowly with hot, dilute
1. Identify the least active metal in the acids.
following list. A Tin
A Calcium B Gold
B Tin C Iron
C Iron D Silver
D Aluminium
4. Use the activity series to identify the most
2. Identify the univalent metal in the following active metal in each of the following lists:
list that reacts with air, water and dilute acid. (a) silver, calcium, aluminium
A Barium (b) nickel, cobalt, gold
B Silver (c) barium, calcium, potassium
C Lead (d) gold, mercury, platinum
D Sodium (e) lead, zinc, magnesium.

CHAPTER 7 METALS AND REACTIONS 131


5. Write balanced chemical equations for the 7. A silvery, divalent metal X reacts with
following reactions involving metals. steam only if the metal is red-hot. The
(a) Steam is passed over red-hot zinc. surface of the metal gradually becomes
(b) Magnesium powder is heated in a jar covered in a black powder. A gas is evolved
of oxygen. in the reaction. This gas explodes in the
(c) Potassium metal is added to dilute presence of a flame.
hydrochloric acid. (a) Identify the gas evolved.
(d) Magnesium metal is added to dilute (b) Write a balanced equation for the
sulfuric acid. reaction of red-hot X with steam.
(c) Identify X from the following list: Al, Mg,
6. Write half-equations and ionic equations for
Fe, Ca, Ag. Justify your answer.
the following:
(a) calcium + dilute sulfuric acid
(b) zinc + dilute hydrochloric acid
(c) potassium + dilute sulfuric acid.

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Remember Relating reactivity to use
Before beginning this section, Knowledge of a metal’s reactivity is important in designing ways to use it. If
you should be able to: a metal readily oxidises (corrodes), it is unsuitable as a structural material
• explain the relationship
between the reactivity of an unless it can be protected from the environment. New metals and alloys are
element and the likelihood of constantly being investigated. Titanium is one example. It has an activity
it existing as an uncombined similar to aluminium but it has greater tensile strength. It can withstand
element
• describe observable changes shearing forces for a longer time than many conventional metals.
when metals react with dilute Titanium alloys are used in the engines of commercial jets. The chemi-
acid, water and oxygen.
cal industry makes increasing use of titanium because of its resistance to
Key content corrosion. Pumps, pipes and reaction vessels made of titanium are used in
By the end of this section, you
should be able to: some chemical industries.
• outline examples of the
selection of metals for
different purposes based
on their reactivity, with
a particular emphasis on
current developments in the
use of metals
• identify the importance of
first ionisation energy in
determining the relative
reactivity of metals
• outline the relationship
between the relative activities
of metals and their positions
in the periodic table
• present information clearly
and succinctly using a variety
of pictorial representations to
show relationships.

Figure 7.6
The fuel tanks on Skylab space
station were made of titanium.

132 METALS
Table 7.5 lists some common uses of metals that are related to their
chemical reactivity. Other uses are related to their physical properties.

Table 7.5 Uses of metals related to their chemical reactivity

Metal Property Use related to property

Mg, Al high reactivity with oxygen fireworks


producing a very bright,
Figure 7.7 white light
A worker inspects hot, galvanised,
sheet steel at a steelworks. The zinc
layer prevents the steel from rusting Ti high corrosion resistance surgical implants
even if the surface is scratched.
Zn more readily oxidised than • galvanised iron. Iron sheeting is
iron or steel protected from rusting by the more
galvanised: describes a metal active zinc.
(such as iron) coated with zinc
to protect it from corrosion • sacrificial anodes. Zinc anodes protect
ship propellers and hulls.

Sn not as readily oxidised as tin plating of steel cans. If no iron is


Iron iron or steel exposed, the less reactive tin protects the
iron.

Zinc coating protects the Cu high corrosion resistance water pipes, electrical wires and wrapping
iron from rusting.
for optic fibre cables. Copper does not
Figure 7.8 corrode readily in the environment.
The zinc coating on galvanised iron
protects the metal from corrosion.

SAMPLE PROBLEM 7.1 Account for the use of calcium rather than copper as a dehydrating
agent for some petroleum solvents.

Calcium is a very active metal that reacts with water and removes it
SOLUTION from the organic solvent. Copper is very unreactive and does not
remove water from the solvent.

Ca(s) + 2H2O(l) Ca(OH)2(s) + H2(g)

Ionisation energy
The reactivity of metals is related to their tendency to lose valence elec-
trons to form ions that have a stable electron configuration. The tendency
of gaseous atoms to lose electrons is measured by a quantity called the
ionisation energy (I ). This energy must be supplied to overcome the
ionisation energy: the minimum attractive force that binds the electrons to the nucleus.
energy required to remove an
electron completely from a Electrons can be removed sequentially according to the strength of the
gaseous atom force that binds them to the nucleus. The energy required to remove the
most loosely bound electron is called the first ionisation energy (I1). The
successive ionisation energies (I1, I2, I3 etc.) reflect the positions of the
electrons in their shells.
Ionisation energies are measured in the gaseous state as the symbol (g)
indicates in the following examples for an element E.

CHAPTER 7 METALS AND REACTIONS 133


First ionisation (I1): E(g) E +(g) + e–

Second ionisation (I2): E +(g) E 2+(g) + e–

Third ionisation (I3): E 2+(g) E 3+(g) + e–

An element such as sodium (Z = 11) has 11 electrons arranged in


3 electron shells. The total number of ionisations for sodium is 11. The
successive ionisation energies increase as each electron is removed.
The factors that affect the ease of removal of electrons from atoms are
the:
• size of the nuclear charge
• distance of the electrons from the nucleus
• presence of shielding inner electrons.
Example 1: Lithium (Z = 3)
Figure 7.9 relates the ionisation energy for each electron in a lithium
atom to its position within the electron shells.
Lithium atoms have three electrons. There is one valence electron in
the L shell. This electron is the easiest
to remove as the L shell is further from
Third electron
Ionisation energy (MJ/mol)

the electrostatic attraction of the posi-


12 removed from K shell
Li 2+ Li 3+ + e– tive nucleus. The L shell electron is also
10
shielded from the nucleus by the inner
8 Second electron
removed from K shell K shell K shell electrons. The second ionisation
6 Li + Li 2+ + e– 4n 7 Li energy (I2) is greater than the first (I1)
3p 3 as the electron has to be removed from
4
First electron
L shell a positive ion (Li+) rather than a neutral
2 removed from L shell
Li Li + + e– atom (Li). The electrons in the K shell are
0 1 2 3 harder to remove as they are closer to the
Electrons removed nucleus so there is a greater electrostatic
Figure 7.9 attraction. Lithium typically exhibits a
Ease of removal of electrons from +1 valency in all its compounds, such as
the K and L shells in lithium
LiBr and Li2O, because of the ease of
removal of the L shell electron.
Example 2: Nitrogen (Z = 7)
Nitrogen has an electron configuration of 2, 5. The five valence electrons
in the L shell are easier to remove from the atom than the inner K shell
electrons, as shown by the data in table 7.6. Plotting this data shows that
the first five ionisation energies increase fairly regularly, but the last two
are significantly higher.

Table 7.6 Successive ionisation energies for nitrogen (MJ/mol)

I1 I2 I3 I4 I5 I6 I7

1.4 2.9 4.6 7.5 9.5 53.3 64.4

Comparing the ionisation energy of metals


Electron transfer reactions occur when metals react with acids. In this
case, however, the electron transfer occurs in an aqueous solution and not

134 METALS
in the gaseous state. We now need to consider the possibility that the ioni-
1000 sation energy of a gaseous metal atom may be related to the activity series.
Table 7.7 shows the first ionisation energy data for selected metals.
900
I1, First ionisation energy (kJ)

Table 7.7 First ionisation energy of selected metals


800
Metal K Na Mg Zn Fe Cu Ag Au
700 I1 (kJ) 425 502 744 913 766 752 737 896

600
This table shows that very reactive metals, such as potassium and sodium,
500 have very low ionisation energies and that magnesium and zinc, which
are less reactive than sodium, have higher ionisation energies. Beyond this,
400 however, the data does not show a simple relationship between the activity
series and ionisation energy. Other factors come into play when determining
0 the relative reactivity of metals.
K Na Mg Zn Fe Cu Ag Au
Relative activity
Decr Reactivity and the periodic table
activity
Figure 7.11 compares the positions of the metals in the activity series with
Figure 7.10 their locations in the periodic table. The following observations can be
Relationship between first ionisation
made:
energy and relative activity
of selected metals • The most active metals, such as potassium and sodium, are in group
I on the left side of the table. In general, their reactivity increases down
the group. Thus, caesium and francium are highly reactive metals.
• The next most active metals, such as calcium and magnesium, belong in
group II. Again, reactivity increases down the group.
• Metals of moderate reactivity, such as zinc and iron, lie at the edge of
the metal zone of the periodic table.
• There is no general pattern for the remaining elements, except that the
least reactive, such as gold and mercury, are located in the lower central
region called the transition metals. Other metals in this region, such as
osmium, iridium and platinum, are also quite unreactive.

I II III IV V VI VII VIII

Moderately reactive metals


(Al, Cr, Zn Fe, Co, Ni)

Figure 7.11
Metal reactivity and the Very reactive metals Unreactive metals Low reactivity, soft metals
periodic table (K, Na, Ba, Ca, Mg) (Hg, Ag, Pt Au) (Sn, Pb)

As previously stated, the reactivity of metals in groups I and II increases


down the group. This is related to the decreasing first ionisation energies
down each group. This, in turn, is related to the increasing distance of
the valence shell from the nucleus. Figure 7.12 shows the decrease in first
ionisation energy with increasing reactivity for group I metals.

CHAPTER 7 METALS AND REACTIONS 135


I1, Ionisation energy (kJ)

600

500

400

300

0
Li Na K Rb Cs
Group I metals
Increasing
activity

Figure 7.12
Relationship between first ionisation
energy of group I metals
and reactivity

Figure 7.13
Copper is an unreactive metal that is highly ductile and has a high electrical conductivity.

7.2 QUESTIONS 3. Titanium and titanium alloys are being


used increasingly in many industries and
1. Select the correct statement about metal applications because
reactivity and the periodic table. A titanium is a lightweight metal with high
A The most reactive metals are the tensile strength and high resistance to
transition metals. corrosion.
B Group III metals are less reactive than B they are more reactive than magnesium
group II metals. and can be used to protect other metals.
C Soft metals in group IV are more reactive C titanium is very cheap to manufacture.
than soft metals, such as aluminium, in D titanium is inert, dense and strong.
group III.
D The least reactive metals in the periodic 4. Tin is suitable for plating steel can because
table are found at the bottom of groups A tin is less dense than iron.
V and VI. B tin is less reactive than iron and protects
2. Identify the number of valence electrons in a it from corrosion.
multi-electron metal atom with the successive C tin is more reactive than iron and
ionisation energies (measured in MJ/mol) corrodes sacrificially.
given in table 7.8. D it is a non-toxic metal that is resistant to
A 1 corrosion in a marine environment.
B 2
Table 7.8 Successive ionisation energies (MJ/mol)
C 3
D 4 I1 I2 I3 I4 I5 I6 I7
0.584 1.823 2.751 11.584 14.837 18.384 23.302

136 METALS
5. Which of the following metals has the (c) Gallium metal also ionises when placed
smallest first ionisation energy? in dilute hydrochloric acid. Write a half-
A Magnesium equation for the ionisation of gallium in
B Sodium this case.
C Aluminium (d) Write the net ionic equation for
D Rubidium the reaction of gallium with dilute
hydrochloric acid.
6. Gallium is chemically similar to aluminium.
(a) Gaseous gallium atoms can be ionised 7. The successive ionisation energies
in three successive steps to form the (in MJ/mol) for two multi-electron elements
stable Ga3+(g) ion. Write each of the half- X and Y are shown in table 7.9:
equations for the stepwise ionisation. (a) Use this data to determine the number of
(b) Identify the ionisation step that requires valence electrons for each element.
the greatest amount of energy. Justify (b) Classify X and Y as metals or non-metals.
your response. Justify your answer.
(c) Predict the chemical formula of a
compound formed between X and Y.
Table 7.9 Successive ionisation energies (MJ/mol)
X 0.60 1.15 4.92 6.48 8.15 10.50 12.33 14.21 18.19 20.39 57.06 63.34

Y 1.26 2.30 3.83 5.16 6.55 9.37 11.03 33.61 38.61 43.97 51.07 57.10

SUMMARY
• Metals react with dilute hydrochloric or sulfuric acid to release
www.jaconline.com.au/chemnsw/chemistry1
hydrogen gas and form ionic salts.
• The order of the activity of metals can be determined by the rate
at which they react with other substances including oxygen, water
and dilute acids.
• The ease or difficulty of thermal decomposition of metallic
compounds can be related to the activity series.
• The most reactive metals are located in groups I and II of the
periodic table. The least reactive metals are located in the lower
periods of the transition metals.
• The reactivity of metals can be understood in terms of the ease
with which they lose electrons. The reactivity of metals is related to
their uses.
• Ionisation energy is the energy required to remove successive
electrons from gaseous atoms.

CHAPTER 7 METALS AND REACTIONS 137


PRACTICAL ACTIVITIES

7.1
Analysing second-hand data
PRACTICAL
ACTIVITIES The following second-hand data is supplied for you
to analyse.
THE ACTIVITY SERIES Part C: Reaction with oxygen (air)
OF METALS Table 7.10 shows the effect of heating a strip of
each metal in air in a Bunsen burner flame.

Table 7.10 Effect of heating metal strips in a Bunsen burner


Aim flame
To gather first-hand data and use supplied second- Metal Observations
hand data to rank metals in order of their activity
Cu surface of strip darkens slowly on heating
Safety issues Zn surface becomes covered in a white powder
• Wear safety glasses throughout this experiment. Mg strip burns with a brilliant white flame, forming
• Identify other safety issues relevant to this white, crumbly powder
experiment by reading the method.
Fe strip glows and changes colour to a dull grey
Materials
• 4 test tubes Part D: Thermal decomposition of metal carbonates
Table 7.11 shows the effect of heating carbonates of
• hot-water bath the selected metals to 1000 °C.
• hotplate
• 250 mL of 2 molL sulfuric acid Table 7.11 Effect of heating metal carbonates to 1000 °C
• small strips of each of selected metals: Cu, Zn, Metal
Mg and Fe carbonate Observations
CuCO3 green powder rapidly turns black; a
Method colourless gas evolves rapidly; gas gives a
Gathering first-hand data positive limewater test
Part A: Reaction with dilute hydrochloric acid ZnCO3 white powder does not change colour;
1. Place a small sample of each metal in a separate colourless gas evolves; gas gives a positive
test tube. limewater test
2. Add about 2–3 mL of dilute acid and observe
MgCO3 white powder does not change colour;
any reactions.
colourless gas evolves slowly; gas gives a
3. Repeat the experiment at a higher temperature positive limewater test
by placing the tubes in a hot water bath and
note any changes after 10–15 minutes. (The FeCO3 grey-green powder turns black; colourless
water in the bath can be boiled and then the gas evolves quickly; gas gives a positive
heat turned off. There is no need to continue limewater test
boiling.)
Two other metal carbonates were also tested for
Part B: Reaction with water thermal decomposition. The results are listed below:
1. Use water instead of acid to test the reactivity of • sodium carbonate — no changes observed; no
each metal as in part A. gases evolved
2. After observing reactions at room temperature, • silver carbonate — yellow powder turns black
place the tubes in a hot-water bath and note any on heating; gases evolved that give a positive
further changes. limewater test and rekindles a glowing splint.

138 METALS
PRACTICAL ACTIVITIES
Results and analysis 4. (a) Identify the gas that produces a positive
glowing splint test.
1. Use your tabulated results of parts A and B
(b) Use the data on sodium carbonate
to rank (where possible) the selected metals
and silver carbonate as well as your
from most reactive to least reactive.
experimental results to establish an activity
2. Process the data from part C and explain series for Cu, Zn, Mg, Fe, Na and Ag.
whether it is consistent with your ranked order (c) Write a balanced chemical equation
established in parts A and B. for the thermal decomposition of silver
3. Examine the data in table 7.11. carbonate based on the experimental data.
(a) Identify the gas that produces a positive
limewater test.
Conclusions
(b) Explain whether the data is consistent with Write a brief conclusion for this experiment.
the following generalisation:

“The more active the metal, the more thermally stable


its carbonate.”

CHAPTER 7 METALS AND REACTIONS 139

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