London is predicted to be hotter than the Caribbean, the Western Sahara and popular holiday destinations in Europe as temperatures soar.
The Met Office has forecast the capital could see highs of 38C when the heatwave sweeps across England.
Record temperatures are also predicted for Scotland, where Nicola Sturgeon has warned people to "look out for others who may be suffering from the heat."
She also asked people to "keep out of direct sun and stay well hydrated" with thr thermometer predicted to reach 32C inEdinburgh and parts of southern Scotland.
The Met Office extended its warning of extreme heat to cover Fife, the Lothians and parts of Tayside yesterday.
☀️ The next couple of days are set to be exceptionally hot. Please take care and follow sensible advice - keep out of direct sun; stay well hydrated; and look out for others who may be suffering from the heat. https://t.co/ecOyCxpMXy
— Nicola Sturgeon (@NicolaSturgeon) July 17, 2022
An amber weather warning was already in place for much of southern Scotland on Monday and Tuesday.
Forecasters have warned people in Dundee, Edinburgh, the Lothians, Fife, Perth, Clackmannanshire, Falkirk and eastern parts of Lanarkshire to expect potentially record temperatures.
While these areas will see more extreme temperatures, the Met Office has said it will be warm across much of the country, especially up the east coast to the Moray Firth.
The amber warning is in place between 00.00 on Monday 18 July to 23.59 on Tuesday 19 July, when cooler Atlantic air should help return the temperature "to more normal values."
The rise in temperatures has forced the UK Health Security Agency to issue a level 4 heat-health alert – described as an “emergency” – while the Met Office has issued the UK’s first red extreme heat warning, with both running from Monday to Wednesday.
London's scorching temperatures mean it will be warmer than Nassau in the Bahamas (32C), Kingston in Jamaica (33C), Malaga in Spain (28C), Athens in Greece (35C), Albufeira in Portugal (28C) and Dakhla, in the Western Sahara (24C).
Other areas of England will also experience hotter weather than the holiday destinations, with the Midlands predicted to see highs of 37C, East Anglia with 36C and the North West and North East with 33C.
It comes as new records were broken in Wales and Northern Ireland on Sunday.
Hawarden, a village in northern Wales, reached 33C while Armagh in Northern Ireland was 27.7C.
Tuesday is meanwhile predicted to be even hotter, with temperatures possibly reaching 40C – a new record for England.
Scientists at the Met Office have said the 40C prediction is a result of climate change, warning that the 40C figure “could be as much as 10 times more likely in the current climate than under a natural climate unaffected by human influence”.
Some schools in several counties, including Nottinghamshire and Hampshire, have confirmed they will close, while train companies urged people not to travel on Monday and Tuesday.
Network Rail will close the East Coast Main Line between noon and 8pm on Tuesday for all locations between London King’s Cross and York and Leeds, with passengers warned not to travel.
Sam MacDougall, operations director for Network Rail said: “Closing the line to traffic is always a last resort but it is the right thing to do to keep people safe on Tuesday given the unprecedented heatwave forecast.
“The forecast temperatures are well above those which our infrastructure is designed for, and safety must come first.”
Additional contingency support for ambulance services, such as more call handlers and extra working hours, have been put in place while the chairman of the NHS Confederation said hospitals are going to be “really, really pushed” over the next few days.
Britons are being urged to stay inside during the hottest points of the day, between 11am and 4pm, and wear sun cream, a hat, stay in the shade and keep hydrated with water.
Emergency services have also urged people to be cautious when cooling off after the body of a boy was recovered in Salford Quays, Greater Manchester, in the early hours of Sunday morning.
A search is meanwhile under way after reports of concern were made for a man seen in a river in Northumberland on Sunday.
Keith Brown, the Scottish Government’s minister for resilience, said the government's resilience arrangments had been activated.
He said: “We are aware of the extension to the weather warnings currently in place and are receiving regular updates from partners including the Met Office and emergency services.
"Our resilience arrangements have been activated and stand ready at all times to coordinate a response to severe weather issues where required. We will continue to closely monitor developments.
“When temperatures increase, it’s important to monitor forecasts and follow public health advice, including staying hydrated and drinking plenty of fluids and avoiding excess alcohol.
“I would also urge people to look out for vulnerable family, friends and neighbours, as older people, those with underlying conditions and those living alone may struggle to keep cool and hydrated.
“Water safety incidents and drownings increase in hot weather and people should be aware of the dangers and use supervised beaches and pools when possible – follow the Water Safety Code and in an emergency call 999.
“If you are planning on travelling to the areas covered by the Red warning, you should be prepared for significant disruption and may want to consider delaying your travel. If you decide to travel, you should prepare appropriately, and keep-up to date with travel alerts.”
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