In her heat of the women's 60m in the morning session, Kemppinen set a new national record of 7.16 seconds as she finished in third place.
Having made a strong start, she was passed by Jamaica's Brianna Lyston and the USA's Jacious Sears, but held off the fast-finishing Philina Marianne Schwartz of Germany to take the final automatic qualification place.
Taking part in the second semi-final when she returned in the evening, Kemppinen could not match that same pace, putting in a 7.19, which was only good enough for sixth place in a race won by Zaynab Dosso of Italy in 7.00, ahead of Great Britain's Dina Asher Smith (7.03).
With only the fastest two in each semi-final and the two quickest non-automatic qualifiers advancing, the Helsinki native was eliminated and unable to add to the European Indoor silver medal she won at the same arena in 2021.
First on the track in the morning session were the men's 60m hurdles heats, which saw Santeri Kuusiniemi go in heat four. Despite clipping the second barrier, he maintained his composure to record a time of 7.75, just 0.05 off his personal best, yet it was only enough for fifth place.
Kuusiniemi was sat in the sixth and final non-automatic qualifying position, until the very next heat when he was eliminated by compatriot and national champion Elmo Lakka, who also finished fifth but in 7.70 seconds, putting him fifth in the list of non-automatic qualifiers.
Only the top four in the final heat went quicker than Lakka, meaning the Finn had qualified for the evening's semi-finals by one hundedth of a second.
In the second semi-final, Lakka was given something of a boost when Milan Trajkovic of Cyprus false-started, but hopes of an upset were dashed when Lakka hit the third barrier in a quick semi-final, finishing seventh in 7.74, as Trey Cunningham of the USA won in a personal best time of 7.35.