OK, I think the conversion is what's making it confusing, so let's clear that out of the way first!
You know that 1 mi took 25 min to walk and you also know that 1 mi equals 1.61 km. So instead of saying 1 mi, say 1.61 km because they're equal (it's much like saying "I watched T.V. for 60 min" instead of "I watched T.V. for 1 hr"...it's just worded differently).
Now the relationship is: 1.61km in 25 min. However, you were asked how long would it take to walk 5 km. So we can set up a proportion.
Here is how you would set it up: you would have both the numerator and denominator having the same unit while the fraction represents one object.
For this proposed problem I would set up one of the fractions for the given walking rate. The numerator would have the km over time as the denominator. The other fraction would have the 5 km over the unknown time it would take. This makes it so the numerators have the same unit (distance in km) while the denominators also share a unit (time in min).
Here are the fractions with the numbers in place: 1.61km/25 min = 5km/x min. So now to solve for x, you cross multiply. This is done by making a zigzag pattern with the math by multiplying diagonally first before dividing the numbers so you would end up at the spot where x would be. So here, you would multiply 5 by 25 (which is 125) and then divide by 1.61. The answer here when rounded would be 77.64 min (125÷1.61≈77.64 min).
This should make sense: 1.61 is roughly a third of 5 so if the distance was three times as much, then the time should be 3 times greater than before.