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Calling the fire service in the event of a fire is an important and urgent thing to do. You need to ensure that they have been called so if you ask someone else to make the call, make sure that they have actually done it. If in doubt call again. It is better to make two calls than to not make any.
The number you call in the UK is 999 or you can also call the European number of 112. Calling 999 or 112 will connect you to the emergency services where they will ask you what service you require. State what you want. It will be at least the fire service but you may also need Police or an ambulance.
The emergency services will ask you where you are, what has happened is anyone trapped, are there any dangerous substances, is anyone hurt, is life at risk. They may also have other questions for you. Try to stay calm and answer the questions fully and clearly.
Once the call has been made you carry on the job of ensuring everyone is in the right place and out of the way when the fire service arrive.
Once you have called the emergency services you need to ask people to direct the fire service to the correct place.
You need to communicate with the emergency services when they arrive to make sure they know where the fire is and any other concerns you have.