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The UK "cannot and will not just look away" at Russia's "hideous and barbaric" attack on Ukraine, Boris Johnson has said.
The PM said President Vladimir Putin had launched a "vast invasion by land, by sea and by air" without provocation.
He said the UK and allies will launch a "massive package" of sanctions to "hobble" Russia's economy.
The PM will outline new sanctions against Russia in the Commons at 17:00 GMT.
In a pre-recorded TV statement, Mr Johnson said Ukraine was not some faraway country, but one "that for decades has enjoyed freedom and democracy and the right to choose its own destiny".
He said the UK and the world could not allow that freedom "just to be snuffed out".
"Our mission is clear: diplomatically, politically, economically and eventually militarily, this hideous and barbaric venture of Vladimir Putin must end in failure," he said.
Mr Johnson's address to the nation comes after Russian forces launched an assault on Ukraine, crossing its borders and bombing military targets near big cities.
Martial law - which means the military takes control temporarily - has been imposed across the whole of Ukraine and people have been trying to flee the capital Kyiv, with traffic jams and crowds seeking shelter in the city's underground.
Russian military vehicles are reported to have breached Ukraine's border in a number of places, in the north, south and east, including from Belarus.
At least seven people are known to have been killed by Russian shelling, including civilians. A Ukrainian presidential adviser said that more than 40 soldiers had died and dozens more were wounded, but this has not been independently confirmed.
Addressing the Ukrainian people directly, Mr Johnson said: "In this moment of agony, we're with you, we're praying for you and your families and we are on your side."
But he said if the months ahead were "grim and the flame of freedom burn[ed] low", he was firmly believed it would "blaze bright again in Ukraine".
"Because for all his bombs and tanks and missiles, I don't believe that the Russian dictator will ever subdue the national feeling of the Ukrainians and their passionate belief that their country should be free," added.