Electrochemistry · ⁨전기화학⁩

Electrolysis 电解 is the breaking down (decomposition 分解) of an ionic compound 离子化合物 — when it is molten 熔融 or in aqueous 水溶液 solution — by passing an electric current 电流 through it.

It only works when the substance is molten or dissolved, because then the ions 离子 are free to move and carry the charge. A solid ionic compound cannot be electrolysed because its ions are locked in place.

The electrolytic cell

The set-up is called an electrolytic cell 电解池. Two electrodes 电极 (solid conductors) dip into the electrolyte 电解质 — the molten or aqueous substance being broken down.

• The anode 阳极 is the positive ($+$) electrode.
• The cathode 阴极 is the negative ($-$) electrode.

The electrodes are often inert 惰性 (they do not react), such as platinum 铂 or carbon/graphite 石墨.

What is formed at each electrode

There is a simple rule:

• Metals 金属 or hydrogen 氢气 are formed at the cathode.
• Non-metals 非金属 (other than hydrogen) are formed at the anode.

For aqueous solutions, the product can depend on whether the solution is dilute 稀 or concentrated 浓. Here are the three Core examples:

Worked example. Predict the products of electrolysing molten zinc chloride, $\text{ZnCl}_2$. Because it is molten, only zinc ions and chloride ions are present - there is no water to complicate things. Zinc is a metal, so it forms at the cathode: $\text{Zn}^{2+}$ ions gain electrons and silvery zinc appears. Chlorine is a non-metal, so it forms at the anode: pale green chlorine gas bubbles off. Always check the state first. A molten compound simply gives you its own two elements, while an aqueous one brings water into the competition - which is why concentrated sodium chloride solution gives hydrogen at the cathode rather than sodium.

How the charge moves

During electrolysis:

• Electrons 电子 move through the wires (the external circuit 外电路) from the power supply.
• At the cathode, positive ions gain electrons. Gaining electrons is reduction 还原.
• At the anode, negative ions lose electrons. Losing electrons is oxidation 氧化.
• Inside the electrolyte, the ions move: positive ions go to the cathode and negative ions go to the anode.

You can write a half-equation 半反应式 for each electrode. For molten lead(II) bromide:

Electrolysis of copper(II) sulfate

The product at the anode depends on the electrode:

• With inert carbon electrodes: copper 铜 forms at the cathode and oxygen forms at the anode. The blue colour of the solution slowly fades as copper is removed.
• With copper electrodes: copper forms at the cathode, while the anode itself dissolves into the solution. The blue colour stays the same. This is used to purify copper.

Electroplating

Electroplating 电镀 means covering a metal object with a thin layer of another metal. This improves its appearance and its resistance to corrosion 腐蚀 (rusting and wearing away).

To electroplate an object:

• the object to be coated is made the cathode;
• the plating metal is made the anode;
• the electrolyte is a solution containing ions of the plating metal.

A fuel cell 燃料电池 uses hydrogen and oxygen to make electricity directly. The only chemical product is water.

It is useful to compare a fuel cell with a normal petrol (gasoline) engine in a vehicle.

Advantages of the fuel cell: the only product is water, so it does not pollute the air, and it changes chemical energy into electricity efficiently. Disadvantages: hydrogen is hard to store and transport safely, and producing the hydrogen can still use energy from fossil fuels.

• At the cathode (negative) you get a metal or hydrogen; at the anode (positive) you get a non-metal. Positive ions move to the cathode, negative ions to the anode.
• A molten compound just gives its two elements. An aqueous solution can give something different (concentrated sodium chloride gives hydrogen and chlorine, not sodium).
• Reduction is gain of electrons (at the cathode); oxidation is loss of electrons (at the anode). Remember OIL RIG.
• In a half-equation the atoms and the charges must balance, with the electrons on the correct side: $\text{Pb}^{2+} + 2e^- \rightarrow \text{Pb}$ (cathode).
• To electroplate an object, make it the cathode, make the plating metal the anode, and use a solution containing ions of the plating metal.